CA2232205A1 - Detergent particle - Google Patents
Detergent particle Download PDFInfo
- Publication number
- CA2232205A1 CA2232205A1 CA 2232205 CA2232205A CA2232205A1 CA 2232205 A1 CA2232205 A1 CA 2232205A1 CA 2232205 CA2232205 CA 2232205 CA 2232205 A CA2232205 A CA 2232205A CA 2232205 A1 CA2232205 A1 CA 2232205A1
- Authority
- CA
- Canada
- Prior art keywords
- detergent
- acid
- particle
- weight
- particle according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000002245 particle Substances 0.000 title claims abstract description 145
- 239000003599 detergent Substances 0.000 title claims abstract description 126
- 239000000203 mixture Substances 0.000 claims abstract description 143
- 239000002253 acid Substances 0.000 claims abstract description 74
- 239000004094 surface-active agent Substances 0.000 claims abstract description 67
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000007844 bleaching agent Substances 0.000 claims description 58
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 26
- 239000003513 alkali Substances 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 21
- 239000002736 nonionic surfactant Substances 0.000 claims description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims description 13
- 239000003945 anionic surfactant Substances 0.000 claims description 13
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 12
- 125000000129 anionic group Chemical group 0.000 claims description 12
- 239000012190 activator Substances 0.000 claims description 10
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- 150000004682 monohydrates Chemical class 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 229940071207 sesquicarbonate Drugs 0.000 claims description 2
- 150000004685 tetrahydrates Chemical class 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims 1
- 159000000011 group IA salts Chemical class 0.000 claims 1
- 238000010412 laundry washing Methods 0.000 abstract description 2
- -1 alkali metal percarbonate Chemical class 0.000 description 82
- 150000001875 compounds Chemical class 0.000 description 58
- 239000002243 precursor Substances 0.000 description 38
- 125000000217 alkyl group Chemical group 0.000 description 35
- 150000003839 salts Chemical class 0.000 description 28
- 125000004432 carbon atom Chemical group C* 0.000 description 26
- 239000000047 product Substances 0.000 description 23
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000002518 antifoaming agent Substances 0.000 description 21
- 239000011734 sodium Substances 0.000 description 21
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 20
- 239000003054 catalyst Substances 0.000 description 20
- 229910052708 sodium Inorganic materials 0.000 description 20
- 239000000463 material Substances 0.000 description 19
- 229920001296 polysiloxane Polymers 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 102000004190 Enzymes Human genes 0.000 description 15
- 108090000790 Enzymes Proteins 0.000 description 15
- 229940088598 enzyme Drugs 0.000 description 15
- 239000010457 zeolite Substances 0.000 description 15
- 239000004615 ingredient Substances 0.000 description 14
- 229920000768 polyamine Polymers 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 13
- 150000001204 N-oxides Chemical class 0.000 description 13
- 229910021536 Zeolite Inorganic materials 0.000 description 13
- 239000003352 sequestering agent Substances 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 150000001768 cations Chemical class 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 12
- 235000014113 dietary fatty acids Nutrition 0.000 description 12
- 239000000194 fatty acid Substances 0.000 description 12
- 229930195729 fatty acid Natural products 0.000 description 12
- 150000004965 peroxy acids Chemical class 0.000 description 12
- 229920005646 polycarboxylate Polymers 0.000 description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 11
- 239000004367 Lipase Substances 0.000 description 11
- 108090001060 Lipase Proteins 0.000 description 11
- 102000004882 Lipase Human genes 0.000 description 11
- 150000007513 acids Chemical class 0.000 description 11
- 150000008051 alkyl sulfates Chemical group 0.000 description 11
- 235000019421 lipase Nutrition 0.000 description 11
- 150000004967 organic peroxy acids Chemical class 0.000 description 11
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 229910000323 aluminium silicate Inorganic materials 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000004744 fabric Substances 0.000 description 10
- 150000004665 fatty acids Chemical class 0.000 description 10
- 239000008187 granular material Substances 0.000 description 10
- 229910001385 heavy metal Inorganic materials 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 10
- 239000000344 soap Substances 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 125000002091 cationic group Chemical group 0.000 description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- 108091005804 Peptidases Proteins 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 8
- 239000003093 cationic surfactant Substances 0.000 description 8
- 239000004927 clay Substances 0.000 description 8
- 229910052700 potassium Inorganic materials 0.000 description 8
- 239000011591 potassium Substances 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 108010065511 Amylases Proteins 0.000 description 7
- 102000013142 Amylases Human genes 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 125000002947 alkylene group Chemical group 0.000 description 7
- 229960004106 citric acid Drugs 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 description 7
- 229920000620 organic polymer Polymers 0.000 description 7
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- 235000019418 amylase Nutrition 0.000 description 6
- 238000004061 bleaching Methods 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 6
- JPZROSNLRWHSQQ-UHFFFAOYSA-N furan-2,5-dione;prop-2-enoic acid Chemical compound OC(=O)C=C.O=C1OC(=O)C=C1 JPZROSNLRWHSQQ-UHFFFAOYSA-N 0.000 description 6
- 125000000623 heterocyclic group Chemical group 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
- 241000894007 species Species 0.000 description 6
- FRPJTGXMTIIFIT-UHFFFAOYSA-N tetraacetylethylenediamine Chemical compound CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 0.000 description 6
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 150000001408 amides Chemical class 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- NARVIWMVBMUEOG-UHFFFAOYSA-N 2-Hydroxy-propylene Natural products CC(O)=C NARVIWMVBMUEOG-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 108010059892 Cellulase Proteins 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- TTZMPOZCBFTTPR-UHFFFAOYSA-N O=P1OCO1 Chemical compound O=P1OCO1 TTZMPOZCBFTTPR-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 239000004365 Protease Substances 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 4
- 239000004902 Softening Agent Substances 0.000 description 4
- 108010056079 Subtilisins Proteins 0.000 description 4
- 102000005158 Subtilisins Human genes 0.000 description 4
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 125000002877 alkyl aryl group Chemical group 0.000 description 4
- 229940025131 amylases Drugs 0.000 description 4
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 4
- 150000007942 carboxylates Chemical class 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 229940106157 cellulase Drugs 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000002304 perfume Substances 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 150000004760 silicates Chemical class 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 239000002888 zwitterionic surfactant Substances 0.000 description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 3
- WLDGDTPNAKWAIR-UHFFFAOYSA-N 1,4,7-trimethyl-1,4,7-triazonane Chemical compound CN1CCN(C)CCN(C)CC1 WLDGDTPNAKWAIR-UHFFFAOYSA-N 0.000 description 3
- 239000004382 Amylase Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 102000035195 Peptidases Human genes 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000002280 amphoteric surfactant Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 3
- 150000001860 citric acid derivatives Chemical class 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000008394 flocculating agent Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000003949 imides Chemical class 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 230000002366 lipolytic effect Effects 0.000 description 3
- 210000003141 lower extremity Anatomy 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 150000003138 primary alcohols Chemical class 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- 229940045872 sodium percarbonate Drugs 0.000 description 3
- 235000019832 sodium triphosphate Nutrition 0.000 description 3
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- 239000003760 tallow Substances 0.000 description 3
- UEJBEYOXRNGPEI-UHFFFAOYSA-N 1-(4-chlorophenyl)-2-(methylamino)propan-1-one Chemical compound CNC(C)C(=O)C1=CC=C(Cl)C=C1 UEJBEYOXRNGPEI-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- NZCIWANIJJJEML-UHFFFAOYSA-N 2-methyl-1,4,7-triazonane Chemical compound CC1CNCCNCCN1 NZCIWANIJJJEML-UHFFFAOYSA-N 0.000 description 2
- YGUMVDWOQQJBGA-VAWYXSNFSA-N 5-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-[(e)-2-[4-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound C=1C=C(\C=C\C=2C(=CC(NC=3N=C(N=C(NC=4C=CC=CC=4)N=3)N3CCOCC3)=CC=2)S(O)(=O)=O)C(S(=O)(=O)O)=CC=1NC(N=C(N=1)N2CCOCC2)=NC=1NC1=CC=CC=C1 YGUMVDWOQQJBGA-VAWYXSNFSA-N 0.000 description 2
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 101100201838 Caenorhabditis elegans rsp-6 gene Proteins 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical class OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
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- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- HFNQLYDPNAZRCH-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O.OC(O)=O HFNQLYDPNAZRCH-UHFFFAOYSA-N 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000010367 cloning Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000004700 cobalt complex Chemical class 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 108010005400 cutinase Proteins 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- FEENHYGBCNSOFG-UHFFFAOYSA-N cyclononane Chemical compound [CH]1CCCCCCCC1 FEENHYGBCNSOFG-UHFFFAOYSA-N 0.000 description 1
- 230000001461 cytolytic effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- DUCCPNVOQJMMAN-UHFFFAOYSA-N dimethylamino hexanoate Chemical compound CCCCCC(=O)ON(C)C DUCCPNVOQJMMAN-UHFFFAOYSA-N 0.000 description 1
- XQRLCLUYWUNEEH-UHFFFAOYSA-L diphosphonate(2-) Chemical compound [O-]P(=O)OP([O-])=O XQRLCLUYWUNEEH-UHFFFAOYSA-L 0.000 description 1
- VVYVUOFMPAXVCH-UHFFFAOYSA-L disodium;5-[[4-anilino-6-[2-hydroxyethyl(methyl)amino]-1,3,5-triazin-2-yl]amino]-2-[2-[4-[[4-anilino-6-[2-hydroxyethyl(methyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfonatophenyl]ethenyl]benzenesulfonate Chemical group [Na+].[Na+].N=1C(NC=2C=C(C(C=CC=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(C)CCO)=CC=3)S([O-])(=O)=O)=CC=2)S([O-])(=O)=O)=NC(N(CCO)C)=NC=1NC1=CC=CC=C1 VVYVUOFMPAXVCH-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical class O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- XWENCHGJOCJZQO-UHFFFAOYSA-N ethane-1,1,2,2-tetracarboxylic acid Chemical class OC(=O)C(C(O)=O)C(C(O)=O)C(O)=O XWENCHGJOCJZQO-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 108010093305 exopolygalacturonase Proteins 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 150000002194 fatty esters Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 229940050410 gluconate Drugs 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 125000003147 glycosyl group Chemical group 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical group 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- JEGIFBGJZPYMJS-UHFFFAOYSA-N imidazol-1-yl(phenyl)methanone Chemical compound C1=CN=CN1C(=O)C1=CC=CC=C1 JEGIFBGJZPYMJS-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical class OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical class OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 108010003855 mesentericopeptidase Proteins 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-N methyl sulfate Chemical group COS(O)(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- GWUSZQUVEVMBPI-UHFFFAOYSA-N nimetazepam Chemical compound N=1CC(=O)N(C)C2=CC=C([N+]([O-])=O)C=C2C=1C1=CC=CC=C1 GWUSZQUVEVMBPI-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- SXLLDUPXUVRMEE-UHFFFAOYSA-N nonanediperoxoic acid Chemical compound OOC(=O)CCCCCCCC(=O)OO SXLLDUPXUVRMEE-UHFFFAOYSA-N 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- VSXGXPNADZQTGQ-UHFFFAOYSA-N oxirane;phenol Chemical compound C1CO1.OC1=CC=CC=C1 VSXGXPNADZQTGQ-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229940055076 parasympathomimetics choline ester Drugs 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical class OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 108010064470 polyaspartate Proteins 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- NJKRDXUWFBJCDI-UHFFFAOYSA-N propane-1,1,2,3-tetracarboxylic acid Chemical class OC(=O)CC(C(O)=O)C(C(O)=O)C(O)=O NJKRDXUWFBJCDI-UHFFFAOYSA-N 0.000 description 1
- NJEVMKZODGWUQT-UHFFFAOYSA-N propane-1,1,3,3-tetracarboxylic acid Chemical class OC(=O)C(C(O)=O)CC(C(O)=O)C(O)=O NJEVMKZODGWUQT-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 238000006268 reductive amination reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 108010080511 serum sodium transport inhibitor Proteins 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- QSKQNALVHFTOQX-UHFFFAOYSA-M sodium nonanoyloxybenzenesulfonate Chemical compound [Na+].CCCCCCCCC(=O)OC1=CC=CC=C1S([O-])(=O)=O QSKQNALVHFTOQX-UHFFFAOYSA-M 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- ZUFONQSOSYEWCN-UHFFFAOYSA-M sodium;2-(methylamino)acetate Chemical compound [Na+].CNCC([O-])=O ZUFONQSOSYEWCN-UHFFFAOYSA-M 0.000 description 1
- RPQSWSMNPBZEHT-UHFFFAOYSA-M sodium;2-acetyloxybenzenesulfonate Chemical compound [Na+].CC(=O)OC1=CC=CC=C1S([O-])(=O)=O RPQSWSMNPBZEHT-UHFFFAOYSA-M 0.000 description 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000004026 tertiary sulfonium compounds Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000005208 trialkylammonium group Chemical group 0.000 description 1
- QQOWHRYOXYEMTL-UHFFFAOYSA-N triazin-4-amine Chemical class N=C1C=CN=NN1 QQOWHRYOXYEMTL-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- WCTAGTRAWPDFQO-UHFFFAOYSA-K trisodium;hydrogen carbonate;carbonate Chemical compound [Na+].[Na+].[Na+].OC([O-])=O.[O-]C([O-])=O WCTAGTRAWPDFQO-UHFFFAOYSA-K 0.000 description 1
- 210000001364 upper extremity Anatomy 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
- C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3942—Inorganic per-compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
Abstract
The present invention relates to an agglomerate or extruded detergent particle, comprising perborate component, an acid source and one or more surfactants, for use in detergent compositions which are suitable for use in laundry washing methods.The invention also relates to a process for making the agglomerated or extruded detergent particle.
Description
CA 0223220', 1998-03-16 Deter~ent particle Technicàl Field The present invention relates to an agglomerated or extruded detergent particle,comprising perborate bleach, an acid source and one or more surfactants, for use in detergent compositions which are suitable for use in laundry washing methods. The invention also relates to a process for making the agglomerated or extruded detergent 1 0 particle.
Back~round to the Invention There is a trend amongst commercially available granular detergents towards higher 15 bulk densities and towards granular detergent compositions which have a higher content of detergent active ingredients, such as bleach. Such detergents offer greater convenience to the consumer and at the same time reduce the amount of packaging materials which will, ultimately, be disposed of. However, traditional detergentformulations and processes to produce the final detergent powder are not always 20 satisfactory or suitable for these detergents, with higher active ingredient concentration.
Amongst consumers there is also a need for detergents which provide improved bleachable stain removal. Therefore, in the recent past detergents have been 25 developed which contain various types of bleaches, which can be incorporated at high levels.
The (high density) detergents, comprising high levels of bleach and surfactant can lead to poor solubility properties, arising from low rate of dissolution or the 30 formation of gels, and thus to poor dispensing of the product, either from the dispensing drawer of a washing m~rhine, or from a dosing device placed with the laundry inside the m~chine. This poor dispensing is often caused by gelling of particles, which have high levels of surfactant and/ or bleach, upon contact with water. The gel prevents a proportion of the detergent powder from being solubilized 35 in the wash water which reduces the effectiveness of the powder. This is a particular problem at low water pressures and/or at lower washing temperature.
CA 0223220~ 1998-03-16 EP-A-0 639 637 discloses the replacement of perborate bleach with an alkali metal percarbonate to improve the dispensing profile and dissolution rate of a detergent.
Citrate or mixtures of citrate with sulphate or carbonate can be used to coat the percarbonate bleach.
EP-A-0 639 639 contains a similar disclosure in this respect.
Other ways to improve dispensing include the use of an effervescence system. If the detergent contains an effervescence system then the generation of a gas such as carbon dioxide pushes the particles of the d~lelgelll apart, and prevents them from gelling.
The use of effervescence to improve the dispensability of granular materials has been used extensively in ph~ ceutical preparations. The most widely used effervescentsystem in this respect is citric acid in combination with bicarbonate. The use of this simple effervescent system has also been described for improving the dispersibility of pesticidal compositions for controlling water-borne pests, e.g. GB-A-2,184,946.
EP-A-0 534 525 discloses the use of citric acid with a specified particle size range of 350 to 1500 microns.
US -A-5, 114,647 discloses a s~niti.~ing composition comprising granules of alkali metal carbonate and aliphatic carboxylic acid of a particle size of 150 to 2,000microns.
EP-A-0 333 223 discloses a bathing plepal~lion comprising fumaric acid having anaverage particle size of 50-500 microns.
The Applicants have found that one of the specific problems associated with poor30 dispensing of detergent compositions which contain ble~.~hing agents and particularly perborate monohydrate bleach, is that localised high concentrations of bleach form which may contact the fabric and cause spot bleaching of coloured fabrics. Secondly, poorly dispensed surfactants tend to deposit on the fabric and the machine. This can lead to fabric damage. These problems can be encountered 35 especially with detergent compositions comprising high levels of surfactants and perborate, especially perborate (monohydrate). However, these high concentrations are often required for an optimal stain/soil removal and suspension and bleachable stain removal.
The Applicants now have found that this problem can be solved or reduced when an5 acid source is agglomerated with or extruded along with the surfactants, or a part thereof, and the perborate bleach to form an agglomerated or extruded d~lelgent particle. In the detergent comprising this agglomerated or extruded particle, an alkali source should be present, capable of producing a gas when reaction with the acidic source. We have found that agglomerating or extruding of such an acid source with 10 surfactant(s) and bleach, when there is an alkali source present in the detergent composition, improves the solubility and/or dispersion of the surfactant(s) and the perborate bleach in the wash water and elimin~tes or reduces the problems of fabric damage by high concentrate bleach and of solid detergent particles or surfactants rem~ining in the washing m~chine and on washed clothes. It is believed that the acid 15 reacts rapidly with the alkali in the wash water to release the gas. This helps disperse the perborate bleach and the detergent in general surfactants and minimi~e the formation of high concentrations of bleach and of insoluble clumps.
The improved dispensing of the surfactant(s) and the perborate bleach can amount to 20 an overall improved and more efficient performance.
Furthermore, the detergent residues in the dispensing drawer or dispensing device are reduced.
25 All documents cited in the present description are, in relevant part, incorporated herein by reference.
Summary of the Invention 30 According to the present invention there is provided an agglomerate or extruded detergent particle comprising a perborate component, one or more surfactants and an acid source. Optionally other detergent ingredient can be present in the agglomerate or extrudate. The agglomerated or extruded dt;telgent particle can be included in delelgellts comprising an alkali source capable of reacting with the acid source to 35 produce a gas. According to the present invention there is also provided a process for making the agglomerate or extruded detergent particle.
CA 0223220~ 1998-03-16 Detailed Description of the Invention s A~lomerate or extruded particle The agglomerate or extruded detergent particle of the present invention contains one or more surfactants and an acid source and a perborate component, which are described below.
The amount of each component in the agglomerate or extruded detergent particle can vary depending on the application of the particle and on the nature of the finaldetergent composition comprising the particle. For example, when the particle will be used in a detergent composition comprising one or more of the same ingredients as the particle, the level thereof in the particle can be reduced.
The level of surfactant in the particle is preferably from 15% to 95%, more preferably from 25% to 60%, most preferably from 30% to 50% by weight of the particle.
The level of acid source in the particle is preferably from 1% to 40%, more preferably from 3% to 30%, even more preferably from 5% to 25%, most preferably from 7% to 15% by weight of the particle The level of perborate component in the particle is preferably from 10% to 70%, more preferably from 15% to 50%, most preferably from 20% to 40% by weight of the particle.
Preferably, at least one anionic surfactant is present. In a pl~f~lled embodiment a nonionic surfactant and an anionic surfactant are present. In a further preferred embodiment an anionic and a cationic and optionally a nonionic surfactant are present. When a cationic sllrf~t~nt is present, preferably a silicate or alumino silicate 35 co.~ ing material is present.
CA 0223220~ 1998-03-16 Preferably, magnesium sulphate is present in the particle, preferably at a level of from 0.1% to 8%, more preferably of from 0.2% to 5%, most preferably from 0.3%
to 3% by weight of the particle.
5 Preferably, the particle does not comprise a bleach activator and/ or crystalline layered silicate.
The agglomerate or extruded particle can optionally comprise additional detergent ingredients. Preferred optional ingredients in the particle can be builders (alumino 10 silicates, polymeric carboxylates), an alkali source, bleach activators and bleach catalysts.
Surfactant 15 The level of surfactant in the particle is preferably from 15% to 95%, more preferably from 25% to 60%, most preferably from 30% to 50% by weight of the particle.
When the particle is comprised in a detergent composition, the total level of 20 surfactant in the d~lergellt composition is preferably of from 1% to 90%, preferably 3% to 70%, more preferably 5% to 40%, even more preferably 10% to 30%, most preferably 12% to 25% by weight ofthe detergent composition.
The surfactant in the agglomerate or extruded particle is selected from anionic,25 nonionic and cationic surfactants and mixtures thereof.
Optionally, ampholytic, amphoteric and zwitterionic surfactants can be present in the particle.
30 A typical listing of anionic, nonionic, ampholytic, and zwitterionic classes, and species of these surfactants, is given in U.S.P. 3,929,678 issued to T ~lghlin and Heuring on December 30, 1975. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A list of suitable cationic surfactants is given in U.S.P. 4,259,217 issued to Murphy on March 35 31, 1981.
CA 0223220~ 1998-03-16 Anionic surfactant The agglomerated or extruded detergent particle in accordance with the present invention preferably comprise one or more anionic surfactants. Essentially any 5 anionic surfactants useful for detersive purposes can be comprised in the detergent composition. These can include salts (including, for example, sodium, potassium,ammonium, and substituted ammonium salts such as mono- di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants.
Anionic sulfate surfactants are preferred.
The level of anionic surfactant is preferably from 10% to 95%, more preferably from 20% to 60%, most preferably from 25% to 50% by weight of the particle.
In detergent compositions, comprising the particle, the total level of anionic surfactant is preferably from 2% to 40%, more preferably from 4% to 30%, even more preferably from 5% to 25%, most preferably from 6% to 15% by weight ofthe composltlon.
Other anionic surfactants include the isethionates such as the acyl isethionates, N-20 acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C12-C1 8 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C6-C 14 diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated 25 resin acids present in or derived from tallow oil.
Anionic sulfate surfactant Anionic sulfate surf~t~nt.c suitable for use herein include the linear and branched 30 primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol snlf~tes, alkyl phenol ethylene oxide ether slllf~tes, the Cs-C17 acyl-N-(C1-C4 alkyl) and -N-(C1-C2 hydroxyalkyl) gluc~mine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
CA 0223220~ 1998-03-16 Alkyl sulfate surfactants are preferably selected from the linear and branched primary C 1 o-C 18 alkyl sulfates, more preferably the C1 1 -C 15 branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates.
Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C1o-C1g alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C 1 1 -C l 8, most preferably C 1 1 -C 1 5 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.
A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.
15 Anionic sulfonate surfactant Anionic sulfonate surfactants suitable for use herein include the salts of Cs-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl 20 glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
Anionic carboxylate surfactant 25 Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.
Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH20)X
30 CH2COO-M+ wherein R is a C6 to C 1 8 alkyl group, x ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 % and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHRl-CHR2-O)-R3 wherein R is a C6 to C 18 alkyl group, x is from 1 to 25, R1 and R2 are selected from the group 35 consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of CA 0223220~ 1998-03-16 hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbonatoms, and mixtures thereof.
Suitable soap surfactants include the secondary soap surfactants which contain a5 carboxyl unit connected to a secondary carbon. Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl- 1 -undecanoic acid, 2-ethyl-1 -decanoic acid, 2-propyl-l-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps may also be included as suds suppressors.
Alkali metal sarcosinate surfactant Other suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON
(Rl) CH2 COOM, wherein R is a Cs-C17 linear or branched alkyl or alkenyl group, 15 R1 is a C1-C4 alkyl group and M is an alkali metal ion. Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.
Cationic surfactants 20 Another pr~r~lled surfactant of the invention is one or more cationic surfactants.
Suitable cationic surf~ct~nt~ include the qll~tern~ry ammonium surfactants selected from mono C6-C16, preferably C6-C1o N-alkyl or alkenyl ammonium surfactants wherein the renl~ining N positions are substituted by methyl, hydroxyethyl or hydroxy~ropyl groups. Another pier~ll~ cationic surfactant is an C6-C 18 alkyl or 25 alkenyl ester of an q~l~tçrn~ry ammonium alcohol, such as qll~t~?rn~ry choline esters.
The level of cationic surfactant is preferably from 1% to 20%, more preferably from 2% to 15%, most preferably from 4% to 10% by weight ofthe particle.
30 In detergent compositions, comprising the particle, the level of cationic surfactant is preferably from 0.2% to 20%, more preferably from 0.5% to 15%, even more preferably from 1% to 10%, most preferably from 1% to 5% by weight ofthe composltlon.
CA 0223220~ 1998-03-16 Nonionic surfactant The detergent composition of the present invention preferably contains a nonionic surfactant. Essentially any nonionic surfactant can be used herein.
The level of nonionic surfactant is preferably from 5% to 60%, more preferably from 10% to 45%, most preferably from 15% to 35% by weight ofthe particle.
In detergent compositions, comprising the particle, the level of nonionic surfactant is preferably from 1% to 30%, more preferably from 2% to 25%, even more preferably from 3% to 15%, most preferably from 4% to 12% by weight ofthe composition.
Alkoxylated nonionic surfactant Essentially any alkoxylated nonionic surfactants are suitable herein. The ethoxylated and propoxylated nonionic surfactants are preferred.
Preferred alkoxylated surfactants can be selected from the classes of the nonionic cond~n~tes of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene ~ mine adducts.
Nonionic alkoxylated alcohol surfactant The con-lPnc~tion products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are suitable for use herein.
The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group cont~ining from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
Nonionic polyhydroxy fatty acid amide surfactant Polyhydroxy fatty acid amides suitable for use herein are those having the structural formulaR2CONR1Z wherein: R1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C 1 -C4 alkyl, more CA 0223220~ 1998-03-16 , preferably Cl or C2 alkyl, most preferably Cl alkyl (i.e., methyl); and R2 is a Cs-C3 1 hydrocarbyl, preferably straight-chain Cs-C 19 alkyl or alkenyl, more preferably straight-chain Cg-C 17 alkyl or alkenyl, most preferably straight-chain Cl 1 -C 17 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear 5 hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.
10 Nonionic fatty acid amide surfactant Suitable fatty acid amide surfactants include those having the formula: R6CoN(R7)2 wherein R6 is an alkyl group cont~inin~ from 7 to 21, preferably from 9 to 17 carbon atoms and each R7 is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and -(C2H4O)XH, where x is in the range of from 1 to 3.
Nonionic alkylpolysaccharide surfactant Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group cont~ining from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group cont~ining from 1.3 to 10 saccharide units.
Preferred alkylpolyglycosides have the formula R20(CnH2nO)t(glycosyl)x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The glycosyl is preferably derived from glucose.
CA 0223220~ 1998-03-16 Optional surfactants Amphoteric surfactant 5 Optional amphoteric surfactants for use in the particle or detergent compositions, comprising the particle, include the amine oxide surfactants and the alkyl amphocarboxylic acids.
Suitable amine oxides include those compounds having the formula R3(oR4)XN0(R5)2 wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, cont~ining from 8 to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group C~ g from 2 to 3 carbon atoms, or mixtures thereof, x is from 0 to 5, preferably from 0 to 3; and each R5 is an alkyl or hydroxyalkyl group cont~ining from 1 to 3, or a polyethylene oxide 15 group cont~inin~ from 1 to 3 ethylene oxide groups. Preferred are Clo-Clg alkyl dimethylamine oxide, and Clo 1 8 acylamido alkyl dimethylamine oxide.
A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Conc.
manufactured by Miranol, Inc., Dayton, NJ.
Zwitterionic surfactant Optionally, zwitterionic surfactants can be incorporated into the particle or detergent compositions comprising the particle. These s~ ct~nt~ can be broadly described as 25 derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary ~mines, or derivatives of quaternary ammonium, q~-~t~rn~ry phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
30 Suitable betaines are those compounds having the formula R(R')2N+R2COO-wherein R is a C6-C1g hydrocarbyl group, each Rl is typically C1-C3 alkyl, and R2 is a Cl-Cs hydrocarbyl group. Preferred betaines are C12 18 dimethyl-ammonio hexanoate and the C10-l8 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.
CA 0223220~ 1998-03-16 Acid source In accordance with the present invention, an acid source, or source of acidity, is present in the agglomerate or extruded detergent particle. When comprised in a 5 detergent composition, the detergent composition contains an alkali source, capable of reacting with the acid source to produce a gas. Optionally, the alkali source or part thereof can be comprised in the particle.
The level of the acid source in the particle is preferably from 1% to 40%, more preferably from 3% to 30%, even more preferably from 5% to 25%, most preferably from 7% to 15% by weight of the particle.
In detergent compositions comprising the particle, the level of the source of acidity is preferably present of from 0.1% to 50%, more preferably from 0.5% to 25%, even more preferably from 1% to 12%, most preferably from 1% to 7% weight of the composltlon.
Preferably, 80% or more of the acid source has a particle size in the range of from about 150 microns to about 710 microns, with at least about 37% by weight of the20 acid source having a particle size of about 350 microns or less. In a plef~lled embodiment 100% of the acid source has a particle size of about 710 microns or less.
Alternatively, greater than about 38%, more preferably 38.7%, of the particulate acid source has a particle size of about 350 microns or less.
25 The particle size of the acid source is calculated by sieving a sample of the source of acidity on a series of Tyler sieves. For example, a Tyler sieve mesh 100 corresponds to an ap~ ule size of 150 microns. The weight fractions thereby obtained are plotted against the aperture size of the sieves.
30 The acid source may be any suitable organic, mineral or inorganic acid, or a derivative thereof, or a mixture thereof. The acid source may be a mono-, bi- or tri-protonic acid. Preferred derivatives include a salt or ester of the acid. The source of acidity is preferably non-hygroscopic, which can improve storage stability. However, monohydrates acids can also be useful herein. Organic acids and their derivatives are 35 preferred. The acid is preferably water-soluble. Suitable acids include citric, glutaric, CA 0223220~ 1998-03-16 succinic or adipic acid, monosodium phosphate, sodium hydrogen sulfate, boric acid, or a salt or an ester thereof. Citric acid is especially preferred.
5 Perborate component Another essential ingredient of the agglomerate or extruded detergent particle of the present invention is a perborate component, which is capable of bleaching.
10 The level of perborate component in the particle is preferably from 10% to 70%, more preferably from 15% to 50%, most preferably from 20% to 40% by weight of the particle.
In detergent compositions comprising the particle, the perborate is preferably present at a level of from 1% to 40% by weight, more preferably from 6% to 25% by weight, most preferably from 13% to 20% by weight of the compositions.
The perborate is preferably in the form of a salt, normally in the form of the alkali metal, preferably sodium salt.
The perborate bleach is preferably sodium perborate in the form of the monohydrate or tetrahydrate, which can be represented respectively with the nominal formula NaBO2H2O2 and NaB~2H2~2 3H2o 25 The perborate bleach may be included as the crystalline solid without additional protection. However, ple~lled executions of certain granular compositions utilize a coated form of the perborate bleach which provides better storage stability for the perhydrate salt in the granular product. Suitable coatings comprise inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic 30 materials such as waxes, oils, or fatty soaps.
Source of Alkali In accordance with the present invention, when the agglomerate or extruded 35 detergent particle is present in a detergent composition, an alkali source is generally present in the detergent composition such that it has the capacity to react with the CA 0223220~ 1998-03-16 acid source to produce a gas. Preferably this gas is carbon dioxide, and therefore the alkali is a carbonate, or a suitable derivative thereof.
Optionally, the alkali source, or part thereof can be present in the particle.
The detergent composition comprising the particle of the present invention, preferably contains from about 2% to about 75%, preferably from about 5% to about 60%, most preferably from about 10% to about 30% by weight of the alkali source.When the alkali source is present in the particle, the agglomerate or extrudate preferably contains from about 5% to about 60%, more preferably from 10% to 50%,most preferably from 15% to 35% of the alkali source.
In a preferred embodiment, the alkali source is a carbonate. Examples of pl~r~ dcarbonates are the ~lk~line earth and alkali metal carbonates, including sodium carbonate, bicarbonate and sesqui-carbonate and any mixtures thereof with ultra-fine calcium carbonate such as are disclosed in German Patent Application No. 2,321,001 published on November 15, 1973. Alkali metal percarbonate salts may also be included in the detergent compositions and are also suitable sources of carbonate species and are described below in more detail.
Other suitable sources will be known to those skilled in the art.
The alkali source may also comprise other components, such as a silicate. Suitable silicates include the water soluble sodium silicates with an SiO2: Na2O ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.0 being preferred, and 2.0 ratio being most preferred. The silicates may be in the form of either the anhydrous salt or a hydrated salt. Sodium silicate with an SiO2: Na20 ratio of 2.0 is the most pl~;r~lled silicate.
Alkali metal persilicates are also suitable sources of silicate herein.
Process for makin~ of the a~lomerate particle The agglomerate detergent particle can be prepared via a process comprising the steps of:
i) allmixing one or more detergent surfactants, the perborate component and an acid source and optionally other detergent ingredientsto form a mixture; and CA 0223220~ 1998-03-16 ii) agglomerating the mixture to form agglomerated particles.
Typically, such a process involves mixing an effective amount of powder, including 5 the acid source, with a high active surfactant paste in one or more agglomerators such as a pan agglomerator, a Z-blade mixer or more preferably in-line mixers, preferably two, such as those m~nllf~tllred by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, and Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1, Elsenerstrasse 7-9, Postfach 2050, Germany. Preferably a high shear10 mixer is used, such as a Lodige CB (Trade Name). Most preferably, a high shear mixer is used in combination with a low shear mixer, such as a Lodige CB (Trade Name) and a Lodige KM (Trade name) or Schugi KM (Trade Name). Optionally, only one or more low shear mixer are used. Preferably, the agglomerates are thereafter dried and/ or cooled.
An other agglomeration process involves mixing of various components of the final agglomrate in different stages, using an fluidised bed. For example, a preferredparticle in accord with the present invention can be agglomerated by addition, preferably by spraying on, of nonionic, anionic surf~ct~nt~ and optionally a wax, or 20 mixtures thereof, to the acid source in powdered form and other optional ingredients.
Then, additional components, including the perborate bleach and optinally the alkali source or part thereof, can be added and agglomerated in one or more stages, thus forming the final agglomerate particle.
25 Preferably, no bleach activator and/ or crystalline layered silicate is added to the agglomerate mix in the agglomeration process for making the particle of the invention.
The agglomerate particles may take the form of flakes, prills, marumes, noodles,30 ribbons, but preferably take the form of granules. A plef~lled way to process the particles is by agglomerating powders (e.g. aluminosilicate, carbonate) with high active surfactant pastes and to control the particle size of the resulting agglomerates within specified limits. Typical particle sizes are from 0.10 mm to 5.0 mm in diameter, preferably from 0.25 mm to 3.0 mm in diameter, most preferably from 0.40 35 mm to 1.00 mm in diameter.
CA 0223220~ 1998-03-16 A high active surfactant paste comprising a mix of, typically, from 50% by weight to 95% by weight, preferably 70% by weight to 85% by weight of surfactant, and optionally it can contain an appropriate acid source. The paste may be pumped into the agglomerator at a temperature high enough to m~int~in a pumpable viscosity, but 5 low enough to avoid degradation of the anionic surfactants used. An operating telllpcldlllre of the paste of 50~C to 80~C is typical. Such pastes and methods for making and processing such pastes is for example described in WO 93/03128.
In an especially preferred embodiment of the present invention, the detergent 10 composition has a density of greater than about 600 g/l and is in the form of powder or a granulate.
Process for makin~ the extruded particle 15 Extruded particles can generally be prepared by mixing the various components, optionally addition of powdered components and/or slip additives, forcing the obtained mixture by pressure through the extruder holes of the required diameter or less, cutting of the extruded paste into extrudates (granules) of the required length and rounding the extrudates. WO 91/13678 and WO 91/02047 describe such 20 processes.
In more detail the extruded particles can be made as follows. The detergent ingredients can be mixed into one paste. Preferably, the various detergent components are pre-mixed in dirr~lelll pastes, preferably two, whereby the acid 25 source preferably is present in a dirr~,le.l~ pre-mixed past than the alkali source if present in the particle, especially when the alkaline source is a carbonate or bicarbonate.
In a highly plefcll~d embo~liment one pre-mixed paste comprises the perborate 30 component and part of the surfactant, preferably the anionic surfactant if present, and additional components such as zeolite and cationic surfactant, and one pre-mixedpaste comprises the acid source and part of the surfactant, preferably the nonionic surfactant. The premixed pastes will then be mixed to form one paste.
35 Optionally, water and additional detergent components, such as slip additives, additional bleach, enzymes, optionally bleach activators, stabilisers and soap can be CA 0223220~ 1998-03-16 added to the pre-mixed paste or pastes or to the paste as a whole, simultaneously with or shortly after the mixing process has started.
Preferably the paste obtained is coated with a slip material prior to or simultaneously 5 with the introduction of the paste in the extruder. A variety of compounds are known to be useful herein as slip additives. Preferred slip additives are those compounds which also have a secondary detergent function, such as certain anionic and nonionic surfactants, polymeric polycarboxylates, polyvinyl alcohols.
10 Under pressure (20 bar or more) the paste or coated paste is then passed through the holes (of the extruder) of the required diameter or less, whereafter the extruded granules are cut in to granules of the required length (about 0.1 mm to 2.0 mm, preferably about 0.4 mm to 1.0 mm).
Typical particle diameter sizes (width) are from 0.10 mm to 5.0 mm, preferably from 0.25 mm to 3.0mm, most preferably from 1.00 mm to 2.50.
The viscosity of the paste should be controlled to avoid caçking of the paste in the extruder or during mixing and to avoid the paste from blocking the extruder. By 20 constant ples~ule, the viscosity is best controlled by heating and cooling the paste and/ or the extruder.
Optionally, the obtained extrudates are rounded, to obtain round or spherical particles.
Preferably, the thus obtained particles are dusted with a powder, preferably zeolite, and dried, to form equally shaped granules, and to avoid agglomeration of the granules.
30 Additional ingredients The agglomerate or extruded detergent particle and/ or the detelgell~ compositions, comprising the particle of the invention, may also contain additional ingredients or components. The precise nature of these additional ingredients, and levels of CA 0223220~ 1998-03-16 .
incorporation thereof will depend on the physical form of the final composition, and the precise nature of the washing operation for which it is to be used.
The detergent particle preferably comprises as an additional ingredient one or more S builders, preferably alumino silicates and/ or organic polycarboxylate polymers, alkali sources, bleach activators or bleach catalysts, or mixtures thereof.
The detergent compositions, comprising the particle of the invention, preferablycontain one or more additional detergent components selected from surfactants as10 described above, additional acid sources, additional bleaches, builders, organic polymeric compounds, enzymes, suds suppressors, lime soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors.
Water-soluble builder compound The particle and/ or the detergent compositions of the present invention can contain a water-soluble builder compound, typically present in deLelg~ compositions at a level of from 1% to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% by weight of the composition.
Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, phosphates, 25 and mixtures of any of the foregoing.
The carboxylate or polycarboxylate builder can be monomeric or oligomeric in type although monomeric polycarboxylates are generally plere,~ed for reasons of cost and performance.
Suitable carboxylates cont~inin~ one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates cont~ining two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid 35 and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.
Polycarboxylates Co"t~ il-g three carboxy groups include, in particular, water-CA 0223220~ 1998-03-16 .
soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in British Patent No. 1,389,732, and aminosuccinatesdescribed in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No.
1,387,447.
Polycarboxylates cont~ining four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates cont~ining sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000. Preferred polycarboxylates are hydroxycarboxylates cont~ining up to three carboxy groups per molecule, more particularly citrates.
Borate builders, as well as builders cont~ining borate-forming materials that can produce borate under detergent storage or wash conditions are useful water-soluble builders herein.
Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.
Partially soluble or insoluble builder compound The particle and/ or the detergent compositions of the present invention may contain a partially soluble or insoluble builder compound, typically present in the detergent composition at a level of from 1% to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% weight of the composition.
In the particle, the partially soluble or insoluble builder compound is preferably present at a level of from 5% to 85% by weight, preferably from 15% to 60% by weight, most preferably from 20% to 50% weight of the particle.
CA 0223220~ 1998-03-16 Examples of largely water insoluble builders include the sodium aluminosilicates.
Suitable aluminosilicate zeolites have the unit cell formula Naz[(AlO2)z(SiO2)y].
xH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.
The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the design~tions Zeolite A, Zeolite B, Zeolite P, Zeolite X,Zeolite HS and mixtures thereof. Zeolite A has the formula Na 12 [AlO2) 12 (SiO2)l2] xH2O
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na86 [(Alo2)g6(sio2)lo6]- 276 H2O.
Preferably, the particle of the invention does not comprise a crystalline layered silicate. However, pl~fe~.~d crystalline layered silicates for use in the detegrent compositions herein have the general formula NaMSixO2x+l YH2o wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their p.~palalion are disclosed in DE-A-3417649 and DE-30 A-3742043. Herein, x in the general formula above preferably has a value of 2, 3 or 4 and is preferably 2. The most preferred material is ~-Na2Si20s, available fromHoechst AG as NaSKS-6.
Additional perhydrate bleaches CA 0223220~ 1998-03-16 In addition to the perborate bleach, metal percarbonates, particularly sodium percarbonate is an optional perhydrate which can be incorporated into the particle or detergent composition of the invention. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2CO3.3H2O2, and is available 5 commercially as a crystalline solid.
Potassium peroxymonopersulfate, sodium per is another optional inorganic perhydrate salt of use in the detergent compositions herein.
10 Or~anic peroxYacid bleachin~ system A pl~el~lled feature of detergent compositions of the invention is an organic peroxyacid bleaching system. In one ~efe,l~d execution the bleachin~ system contains a hydrogen peroxide source and an organic peroxyacid bleach precursor 15 compound. The production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches, such as the perborate bleach of the claimed invention. In an alternative p~ef~ d execution a plefollned organic peroxyacid is incorporated directly into the composition. Compositions cont~inin~
20 mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.
Peroxyacid bleach precursor 25 Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be represented as O
X-C -L
where L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is o X-C-OOH
CA 0223220~ 1998-03-16 Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 20% by weight, more preferably from 1% to 15% by weight, most preferably from 1.5% to 10% by weight of the detergent compositions.
Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, which precursors can be selected from a wide range of classes.
Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798,l 147871, 2143231 and EP-A-0170386.
Leaving ~roups 15 The leaving group, hereinafter L group, must be sufficiently reactive for theperhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle).
However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.
25 Preferred L groups are selected from the group consisting of:
--O~ ~~Y and --O~
IR3 ~ ' R3 Y
CA 0223220~ 1998-03-16 R3 r -O--CH=C--CH=CH2 --O--CH=C--CH=CH2 1~l Y 1~l -O--C--R1 --N/ ~NR4 --N /NR4 --O--C=CHR4 , and IN i--CH--R4 R3 o and mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group cont~ining from 1 to 14 carbon atoms, R3 is an alkyl chain cont~ining from 1 to 8 carbon atoms, R4 is H or R3, and Y is H or a solubilizing group. Any of R1, R3 and R4 may be substituted by essentially any functional group including, for example alkyl, 10 hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups.
The preferred solubilizing groups are -SO3 M, -CO2 M, -SO4 M, -N (R3)4X
and o<--N(R3)3 and most preferably -SO3-M+ and -CO2-M+ wherein R3 is an alkyl 15 chain co~ il-g from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.
Alkyl percarboxylic acid bleach precursors Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis. Preferred precursors of this type provide peracetic acid on 25 perhydrolysis.
CA 0223220~ 1998-03-16 Preferred alkyl percarboxylic precursor compounds of the imide type include the N-,N,NlNl tetra acetylated alkylene ~ mines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is 5 particularly preferred. The TAED is preferably not present in the agglomeratedparticle of the present invention, but preferably present in the detergent composition, comprising the particle.
Other p.efel.~d alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl 10 hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
Amide substituted alkyl peroxyacid precursors 15 Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae:
R1~C N~R2 C L R1 N~C~R2- C~L
, O R5 0 or R5 0 0 20 wherein Rl is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene group cont~ining from 1 to 14 carbon atoms, and R5 is H or an alkyl group cont~ining 1 to 10 carbon atoms and L can be essentially any leaving group. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
Perbenzoic acid precursor Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
Suitable O-acylated perbenzoic acid precursor compounds include the substituted and 30 unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products ofsorbitol, glucose, and all saccharides with benzoylating agents, and those of the imide type including N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas. Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole. Other useful N-acyl CA 0223220~ 1998-03-16 group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
Cationic peroxyacid precursors s Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.
Typically, cationic peroxyacid precursors are formed by substituting the peroxyacid 10 part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkyl ammmonium group, preferably an ethyl or methyl ammonium group. Cationic peroxyacid precursors are typically present in the solid detergent compositions as a salt with a suitable anion, such as a halide ion.
The peroxyacid precursor compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof, precursor compound as described hereinbefore. Alternatively, the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid 20 precursor as described hereinafter.
Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015;
4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,382,594;
EP 475,512, 458,396 and 284,292; and in JP 87-318,332.
Examples of pler~ d cationic peroxyacid precursors are described in UK Patent Application No. 9407944.9 and US Patent Application Nos. 08/298903, 08/298650, 08/298904 and 08i298906.
30 Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium 35 methylene alkyl caprolactams.
CA 0223220~ 1998-03-16 Benzoxazin organic peroxyacid precursors Also suitable are precursor compounds of the benzoxazin-type, as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the forrnula:
col [~N"C R1 wherein R1 is H, alkyl, alkaryl, aryl, or arylalkyl.
10 Preformed organic peroxyacid The organic peroxyacid bleaching system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid, typically at a level of from 1% to 15% by weight, more 15 preferably from 1% to 10% by weight of the composition.
A preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae:
O R5 o or wherein Rl is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is an alkylene, arylene, and alkarylene group cont~inin~ from 1 to 14 carbon atoms, and 25 RS is H or an alkyl, aryl, or alkaryl group co~ il-g 1 to 10 carbon atoms. Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.
CA 0223220~ 1998-03-16 , Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-phthaloylaminoperoxicaproic acid are also suitable herein.
Bleach catalyst The particle and/ or the compositions optionally contain a transition metal cont~ining bleach catalyst. One suitable type of bleach catalyst is a catalyst system comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron orm~ng~nese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylene~i~minetetraacetic acid, ethylene~i~minetetra(methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S. Pat. 4,430,243.
Other types of bleach catalysts include the m~ng~n~se-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts include MnIV2(u-O)3(1,4,7-trimethyl- 1,4,7-triazacyclononane)2-(PF6)2, MnIII2(u-O) 1 (u-OAc)2(1,4,7-trimethyl- 1,4,7-triazacyclononane)2-(ClO4)2, MnIV4(u-O)6(1,4,7-triazacyclononane)4-(ClO4)2, MnIIIMnIV4(u-O) 1 (u-OAc)2 (1,4,7-trimethyl-1,4,7-triazacyclononane)2-(ClO4)3, and mixtures thereof. Others are described in European patent application publication no. 549,272. Other ligands suitable for use herein include 1,5,9-trimethyl- 1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl- 1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and mixtures thereof.
For examples of suitable bleach catalysts see U.S. Pat. 4,246,612 and U.S. Pat.
5,227,084. See also U.S. Pat. 5,194,416 which teaches mononuclear m~ng~nese (IV)complexes such as Mn(1,4,7-trimethyl-1,4,7-tri~7~cyclononane)(OCH3)3 (PF6). Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is a water-soluble complex of m~ng~nese (III), and/or (IV) with a ligand which is a non-carboxylatepolyhydroxy compound having at least three consecutive C-OH groups. Other examples include binuclear Mn complexed with tetra-N-dentate and bi-N-dentate lig~n-l~, including N4MnIII(u-0)2MnIVN4)+and [Bipy2MnIII(u-0)2MnIVbipy2]-(C104)3.
CA 0223220~ 1998-03-16 Further suitable bleach catalysts are described, for example, in European patentapplication No. 408,131 (cobalt complex catalysts), European patent applications, publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S. 4,728,455 (m~ng~nese/multidentate ligand catalyst), U.S. 4,711,748 and European patent application, publication no. 224,952, (absorbed m~ng~nese on aluminosilicate catalyst), U.S. 4,601,845 (aluminosilicate support with m~ng~nese and zinc or m~gnesium salt), U.S. 4,626,373 (m~n~nese/ligand catalyst), U.S. 4,119,557 (ferric complex catalyst), German Pat. specification 2,054,019 (cobalt chelant catalyst)10 C~n~ n 866,191 (transition metal-cont~inin~. salts), U.S. 4,430,243 (chelants with m~ng~nese cations and non-catalytic metal cations), and U.S. 4,728,455 (m~ng~nPse gluconate catalysts).
Heavy metal ion sequestrant The particle and or the detergent compositions, comprising the particle of the invention preferably contain as an optional component a heavy metal ion sequestrant.
By heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and 20 magnesium chelation capacity, but pr~rerelltially they show selectivity to binding heavy metal ions such as iron, m~n~nese and copper.
Heavy metal ion sequestrants are generally present at a level of from 0.005% to 20%, preferably from 0.1% to 10%, more preferably from 0.25% to 7.5% and most 25 preferably from 0.5% to 5% by weight of the compositions.
Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy disphosphonates and nitrilo trimethylene phosphonates.
Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene ~ mine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate.
35 Other suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylene~i~minotetracetic acid, CA 0223220~ 1998-03-16 ethylenetriamine pentacetic acid, ethylene~i~rnine disuccinic acid, ethylene~ mine diglutaric acid, 2-hydroxypropylene~ mine disuccinic acid or any salts thereof Especially prer~lled is ethylene.li~-nine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or5 mixtures thereof.
Other suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133. The iminodiacetic acid-N-2-10 hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein. The ,B-alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants described in EP-A-509,382 are also suitable.
EP-A-476,257 describes suitable amino based sequestrants. EP-A-510,331 describessuitable sequestrants derived from collagen, keratin or casein. EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid are also suitable. Glycinamide-N,N'-20 disuccinic acid (GADS), ethylenetli~mine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylene~ min~-N-N'-disuccinic acid (HPDDS) are also suitable.
EnzYme 25 Another plef~lled ingredient useful in the detergent compositions, comprising the particle, is one or more additional enzymes. Optionally, the enzymes or part thereof cam be present in the agglomerated or extruded particle of the invention.
Preferred additional enzymatic materials include the commercially available lipases, 30 cutinases, amylases, neutral and ~lk~line proteases, esterases, cellulases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions.
Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
Preferred commercially available protease enzymes include those sold under the 35 tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denrnark), those sold under the tr~dçn~rne Maxatase, Maxacal and Maxapem CA 0223220~ 1998-03-16 -by Gist-Brocades, those sold by Genencor International, and those sold under thetr~clen~me Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001 % to 4% active enzyme by weight of the composition.
Preferred amylases include, for example, a-amylases obtained from a special strain of B licheniformis, described in more detail in GB-1,269,839 (Novo). Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename 10 Termamyl and BAN by Novo Industries A/S. Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight of the composition.
Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001% to 2% by weight, preferably 0.001% to 1% by weight, most preferably from0.001% to 0.5% by weight ofthe compositions.
The lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp.
20 including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase fromchemically or genetically modified mutants of these strains are also useful herein. A
preferred lipase is derived from Pseudomonas pseudoalcali~enes. which is described in Granted European Patent, EP-B-0218272.
25 Another plefelled lipase herein is obtained by cloning the gene from Humicolal~nu~inosa and ~ressing the gene in Asper~illus oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available fromNovo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.
Or~anic polymeric compound Organic polymeric compounds are preferred additional components of the particle and/ or the d~lel~ ll compositions, comprising the particle in accord with the 35 invention, and are preferably present as components of any particulate components where they may act such as to bind the particulate component together. By organic CA 0223220~ 1998-03-16 polymeric compound it is meant herein essentially any polymeric organic compoundcommonly used as dispersants, and anti-redeposition and soil suspension agents in dete~gent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein.
Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.1 % to 30%, preferably from 0.5% to 15%, most preferably from I % to 10% by weight of the compositions.
10 Examples of organic polymeric compounds include the water soluble organic homo-or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers ofthe lattertype are disclosed in GB-A-1,596,756.
Examples of such salts are polyacrylates of MWt 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 100,000, especially 40,000 to 80,000.
The polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
Terpolymers cont~ining monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.
Other organic polymeric compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.
Further useful organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.
Another organic compound, which is a preferred clay dispersant/ anti-redeposition agent, for use herein, can be the ethoxylated cationic monoamines and ~i~mines of the formula:
CA 0223220~ 1998-03-16 X i OCH2CH2) N+ CH2---CH2~CH2)a b N CH2 2 (CH2CH20 -)~ X (CH2CH20 ~ X
wherein X is a nonionic group selected from the group consisting of H, C1-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof, a is from 0 to 20, preferably from 0 to 4 (e.g. ethylene, propylene, hexamethylene) b is 1 or 0; for cationic mono~mines (b=0), n is at least 16, with a typical range of from 20 to 35; for cationic diamines (b=1), n is at least about 12 with a typical range of from about 12 to about 42.
Other di~l~cr~a~ / anti-redeposition agents for use herein are described in EP-B-10 011965 and US 4,659,802 and US 4,664,848.
Suds suppressing system The detergent compositions, when formulated for use in m~hine washing 15 compositions, preferably comprise a suds suppressing system present at a level of from 0.01% to 15%, preferably from 0.05% to 10%, most preferably from 0.1% to 5% by weight of the composition.
Suitable suds suppressing systems for use herein may comprise essentially any 20 known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds.
By antifoam compound it is meant herein any compound or mi~lulcs of compounds which act such as to depress the foaming or sudsing produced by a solution of a 25 detergent composition, particularly in the presence of agitation of that solution.
Particularly prcf~llcd antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica 30 component. The term "silicone" as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types. Preferred silicone CA 0223220~ 1998-03-16 antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.
Other suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and 10 alkanolammonium salts.
Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C 1 g-C40 ketones (e.g. stearone) N-alkylated amino triazines such as tri- to 15 hexa-alkylmel~mine~ or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine cont~ining 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.
A preferred suds suppressing system comprises (a) antifoam compound, preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination (i) polydimethyl siloxane, at a level of from 50% to 99%, preferably 75%
to 95% by weight of the silicone antifoam compound; and (ii) silica, at a level of from 1% to 50%, preferably 5% to 25% by weight of the silicone/silica antifoam compound;
wherein said silicalsilicone antifoam compound is incorporated at a level of from 5%
to 50%, preferably 10% to 40% by weight;
35 (b) a dispersant compound, most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide CA 0223220~ 1998-03-16 -to propylene oxide ratio of from 1 :0.9 to 1: 1.1, at a level of from 0.5% to 10%, preferably 1 % to 10% by weight; a particularly preferred silicone glycol rake copolymer of this type is DCO544, commercially available from DOW
Corning under the tradename DCO544;
s (c) an inert carrier fluid compound, most preferably comprising a C 16-c 18 ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to 70%, by weight;
A highly plerell~d particulate suds su~plessing system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier m~teri~l having a melting point in the range 50~C to 85~C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain cont~ining from 12 to 20 carbon atoms. EP-A-0210721 discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid oralcohol having a carbon chain cont~ining from 12 to 20 carbon atoms, or a mixture thereof, with a melting point of from 45~C to 80~C.
Clay softening system The particle and/ or the detergent compositions may contain a clay softening system comprising a clay mineral compound and optionally a clay flocculating agent.
The clay mineral compound is preferably a smectite clay compound. Smectite claysare disclosed in the US Patents Nos. 3,862,058, 3,948,790, 3,954,632 and 4,062,647.
European Patents Nos. EP-A-299,575 and EP-A-313,146 in the name of the Procter and Gamble Company describe suitable organic polymeric clay flocculating agents.
Polymeric dye transfer inhibitin~ a~ents The particle, but preferably the detergent compositions may also comprise from 0.01% to 10 %, preferably from 0.05% to 0.5% by weight of polymeric dye transferinhibiting agents.
CA 0223220~ 1998-03-16 The polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof.
S a) Polyamine N-oxide polymers Polyamine N-oxide polymers suitable for use herein contain units having the following structure formula:
(I) Ax R
wherein P is a polymerisable unit, and A is NC, CO, C, -O-, -S-, -N-; x is O or1;
R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-O group can be attached orwherein the nitrogen of the N-O group is part of these groups.
20 The N-O group can be represented by the following general structures:
o o (R1) X-N-(R2) (R3)z or N-(R1 )x 25 wherein R1, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group forms CA 0223220~ 1998-03-16 part of these groups. The N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic,alicyclic or heterocyclic groups. One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline,10 acridine and derivatives thereof.
Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O groupis attached to the polymerisable unit. A pl~rt;,led class of these polyamine N-oxides comprises the polyamine N-oxides having the general formula (I) wherein R is an 15 aromatic,heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said. R group. Examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
20 The polyamine N-oxides can be obtained in almost any degree of polymerisation.
The degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power. Typically, the average molecular weight is within the range of 500 to 1000,000.
25 b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole Suitable herein are coploymers of N-vinylimidazole and N-vinylpyrrolidone havingan average molecular weight range of from 5,000 to 50,000. The plefe,~ed copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 30 0.2.
c) Polyvinylpyrrolidone The delelgellt compositions herein may also utilize polyvinylpyrrolidone ("PVP")35 having an average molecular weight of from 2,500 to 400,000. Suitable polyvinylpyrrolidones are commercially valuable from ISP Corporation, New York, CA 0223220~ 1998-03-16 NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of360,000). PVP K-15 is also available from ISP Corporation. Other suitable 5 polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.
d) Polyvinyloxazolidone 10 The detergent compositions herein may also utilize polyvinyloxazolidones as polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have an average molecular weight of from 2,500 to 400,000.
e) Polyvinylimidazole The detergent compositions herein may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent. Said polyvinylimidazoles preferably have an average molecular weight of from 2,500 to 400,000.
20 Optical bri~htener The detergent compositions herein also optionally contain from about 0.005% to 5%
by weight of certain types of hydrophilic optical brighteners.
25 Hydrophilic optical brighteners useful herein include those having the structural formula:
N~ ~C=C~N~
R2 SO3M SO3M Rl 30 wherein Rl is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl, R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, CA 0223220~ 1998-03-16 morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.
When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is a 5 cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2-methylaminoand M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt. This particular brightener species is commercially marketed under the 15 tr~den~me Tinopal 5BM-GX by Ciba-Geigy Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener species is 20 commercially marketed under the tr~den~me Tinopal AMS-GX by Ciba Geigy Corporation.
Cationic fabric softening agents 25 Cationic fabric softening agents can also be incorporated into the particle and/or the compositions. Suitable cationic fabric softening agents include the water insoluble tertiary amines or dilong chain amide materials as disclosed in GB-A-I 514 276 and EP-B-0 011 340.
30 Cationic fabric softening agents are typically incorporated at total levels of from 0.5% to 15% by weight, normally from 1% to 5% by weight.
Other optional ingredients CA 0223220~ 1998-03-16 Other optional ingredients suitable for inclusion in the particle and the detergent compositions include perfumes, colours and filler salts, with sodium sulfate being a preferred filler salt.
CA 0223220~ 1998-03-16 pH of the compositions The final detergent compositions preferably have a pH measured as a 1% solution in distilled water of at least 10.0, preferably from 10.0 to 12.5, most preferably from 5 10.5 to 12Ø
Form of the a~glomerated or extruded particle and deter~ent compositions thereof Surfactant a~lomerate particles The particles may take the form of flakes, prills, marumes, noodles, ribbons, but preferably take the form of granules. The most ~l~r~ d way to process the particles, as described above, is by agglomerating or mixing and extruding powders (e.g.
aluminosilicate, optionally carbonate) with high active surfactant pastes and to15 control the particle size of the resultant particles within specified limits.
Form of the compositions The compositions, comprising the particle, can take a variety of physical forms 20 including granular, tablet and bar. The compositions can be of the form of the so-called concentrated granular detergent compositions adapted to be added to a washing m~ ine by means of a dispensing device placed in the machine drum with the soiled fabric load.
25 The mean particle size of the base composition of granular compositions in accordance with the invention can be from 0.1 mm to 5.0 mm, but it should preferably be such that no more that 5% of particles are greater than 1 .7mm in diameter and not more than 5% of particles are less than 0.1 Smm in diameter.
30 The term mean particle size as defined herein is calculated by sieving a sample of the composition into a number of fractions (typically 5 fractions) on a series of Tyler sieves. The weight fractions thereby obtained are plotted against the aperture size of the sieves. The mean particle size is taken to be the aperture size through which 50%
by weight of the sample would pass.
CA 0223220~ 1998-03-16 The bulk density of granular detergent compositions is typically of at least 500g/litre, more preferably from 650 g/litre to 1200 g/litre. Bulk density is measured by means of a simple funnel and cup device consisting of a conical funnel moulded rigidly on a base and provided with a flap valve at its lower extremity to allow the contents of the funnel to be emptied into an axially aligned cylindrical cup disposed below the funnel. The funnel is 130 mm high and has internal diameters of 130 mmand 40 mm at its respective upper and lower extremities. It is mounted so that the lower extremity is 140 mm above the upper surface of the base. The cup has an overall height of 90 mm, an internal height of 87 mm and an internal diameter of 84 10 mm. Its nominal volume is 500 ml.
To carry out a measurement, the funnel is filled with powder by hand pouring, the flap valve is opened and powder allowed to overfill the cup. The filled cup is removed from the frame and excess powder removed from the cup by passing a 15 straight edged implement eg; a knife, across its upper edge. The filled cup is then weighed and the value obtained for the weight of powder doubled to provide a bulk density in g/litre. Replicate measurements are made as required.
Laundry washin~ method Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed thereinan effective amount of a m~rhine laundry detergent composition in accord with the invention. By an effective amount of the detergent composition it is meant from 40g 25 to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional m~rhine laundry methods.
In a plefell~d use aspect a dispensing device is employed in the washing method.30 The dispensing device is charged with the detergent product, and is used to introduce the product directly into the drum of the washing machine before the commencement of the wash cycle. Its volume capacity should be such as to be able to contain sufficient detergent product as would normally be used in the washing method.
35 Once the washing machine has been loaded with laundry the dispensing device containing the detergent product is placed inside the drum. At the commencement of CA 0223220~ 1998-03-16 the wash cycle of the washing machine water is introduced into the drum and the drum periodically rotates. The design of the dispensing device should be such that it permits containment of the dry detergent product but then allows release of thisproduct during the wash cycle in response to its agitation as the drum rotates and also as a result of its contact with the wash water.
To allow for release of the detergent product during the wash the device may possess a number of openings through which the product may pass. Alternatively, the device may be made of a material which is permeable to liquid but impermeable to the solid 10 product, which will allow release of dissolved product. Preferably, the detergent product will be rapidly released at the start of the wash cycle thereby providing transient localised high concentrations of product in the drum of the washing machine at this stage of the wash cycle.
15 Preferred dispensing devices are reusable and are designed in such a way thatcontainer integrity is m~int~ined in both the dry state and during the wash cycle.
Especially preferred dispensing devices for use with the composition of the invention have been described in the following patents; GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-0201376, EP-A-0288345 and EP-A-0288346. An article by J.Bland published 20 in Manufacturing Chemist, November 1989, pages 41-46 also describes especially plcfel~cd dispensing devices for use with granular laundry products which are of a type commonly know as the "granulette". Another plcrellcd dispensing device for use with the compositions of this invention is disclosed in PCT Patent Application No. WO94/11562.
Especially ~;,lefellcid dispensing devices are disclosed in European Patent Application Publication Nos. 0343069 & 0343070. The latter Application discloses a device comprising a flexible sheath in the form of a bag extending from a support ring defining an orifice, the orifice being adapted to admit to the bag sufficient product for 30 one washing cycle in a washing process. A portion of the washing medium flowsthrough the orifice into the bag, dissolves the product, and the solution then passes outwardly through the orifice into the washing medium. The support ring is provided with a m~king arrangement to prevent egress of wetted, undissolved, product, this arrangement typically comprising radially e~t~n~ling walls extending from a central 35 boss in a spoked wheel configuration, or a similar structure in which the walls have a helical form.
CA 0223220~ 1998-03-16 .
Alternatively, the dispensing device may be a flexible container, such as a bag or pouch. The bag may be of fibrous construction coated with a water impermeable protective material so as to retain the contents, such as is disclosed in European published Patent Application No. 0018678. Alternatively it may be formed of a water-insoluble synthetic polymeric material provided with an edge seal or closure designed to rupture in aqueous media as disclosed in European published Patent Application Nos. 0011500, 0011501, 0011502, and 0011968. A convenient form of water frangible closure comprises a water soluble adhesive disposed along and sealing one edge of a pouch formed of a water impermeable polymeric film such aspolyethylene or polypropylene.
Packaging for the compositions Commercially marketed executions of the bleaching compositions can be packaged in any suitable container including those constructed from paper, cardboard, plastic materials and any suitable l~min~tPs A preferred pack~gin~ execution is described in European Application No. 94921505.7.
Abbreviations used in following Examples In the detergent compositions, the abbreviated component identifications have the following m~ninp~
LAS : Sodium linear C12 alkyl benzene sulfonate TAS : Sodium tallow alkyl sulfate C45AS : Sodium C 14-C 15 linear alkyl sulfate CxyEzS : Sodium Clx-Cly branched alkyl sulfate condensed with z moles of ethylene oxide C45E7 : A C14 15 predomin~ntly linear primary alcohol condensed with an average of 7 moles of ethylene oxide C25E3 : A C12 15 branched primary alcohol condensed with an average of 3 moles of ethylene oxide C25E5 : A C12 15 branched primary alcohol condensed with an average of 5 moles of ethylene oxide CA 0223220~ 1998-03-16 CEQ : RlCOOCH2CH2.N+(CH3)3 with Rl = C11-C13 QAS : R2.N+(CH3)2(c2H4OH) with R2 = C12 ~ C14 Soap : Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut oils.
TFAA : C 16-c 18 alkyl N-methyl glucamide TPKFA : C12-C14 topped whole cut fatty acids STPP : Anhydrous sodium tripolyphosphate Zeolite A : Hydrated Sodium Aluminosilicate of formula Nal2(A102SiO2)12. 27H20 having a primary particle size in the range from 0.1 to 10 micrometers NaSKS-6 : Crystalline layered silicate of formula o -Na2Si205 Citric acid : Anhydrous citric acid Carbonate : Anhydrous sodium carbonate with a particle size between 200 ~lm and 900~1m Bicarbonate : Anhydrous sodium bicarbonate with a particle size distribution between 40011m and 1200~1m Silicate : Amorphous Sodium Silicate (SiO2:Na2O; 2.0 ratio) Sodium sulfate : Anhydrous sodium sulfate Citrate : Tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution between 425~1m and 850~m MA/AA : Copolymer of 1 :4 maleic/acrylic acid, average molecular weight about 70,000.
CMC : Sodium carboxymethyl cellulose Protease : Proteolytic enzyme of activity 4KNPU/g sold by NOVO Industries A/S under the tradename Savinase Alcalase : Proteolytic enzyme of activity 3AU/g sold by NOVO Industries A/S
Cellulase : Cellulytic enzyme of activity 1000 CEVU/g sold by NOVO Industries A/S under the tr~dçn~me Carezyme Amylase : Amylolytic enzyme of activity 60KNU/g sold by NOVO Industries A/S under the tradename Termamyl 60T
CA 0223220~ 1998-03-16 Lipase : Lipolytic enzyme of activity 1 00kLU/g sold by NOVO Industries A/S under the tradename Lipolase Endolase : Endoglunase enzyme of activity 3000 CEVU/g sold by NOVO Industries A/S
PB4 : Sodium perborate tetrahydrate of nominal formula NaB02.3H20-H202 PB 1 : Anhydrous sodium perborate monohydrate bleach of nominal formula NaBo2.H2o2 Percarbonate : Sodium Percarbonate of nominal formula 2Na2C03 3H202 NOBS : Nonanoyloxybenzene sulfonate in the forrn of the sodium salt.
TAED : Tetraacetylethylene~ mine DTPMP: Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Trade name Dequest 2060 Photoactivated : Sulfonated Zinc Phthlocyanine encapsulated in bleach dextrin soluble polymer Brightener l : Disodium4,4'-bis(2-sulphostyryl)biphenyl Brightener 2 : Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2-yl)amino) stilbene-2:2'-disulfonate.
HEDP : 1,1-hydroxyethane diphosphonic acid PVNO : Polyvinylpyridine N-oxide PVPVI : Copolymer of polyvinylpyrolidone and vinylimidazole SRP 1 : Sulfobenzoyl end capped esters with oxyethylene oxy and terephtaloyl backbone SRP 2 : Diethoxylated poly (1, 2 propylene terephtalate) short block polymer Silicone antifoam: Polydimethylsiloxane foam controller with siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1.
Alkalinity : % weight equivalent of NaOH, as obtained using the alkalinity release test method described herein.
CA 0223220~ 1998-03-16 In the following Examples all levels are quoted as % by weight of the composition:
Example 1 The following detergent formulations according to the present invention were prepared:
A B
Blown Powder Zeolite A 15.0 Sodium sulfate - -LAS 3.0 CEQ 2.0 1.3 DTPMP 0.4 CMC 0.4 MA/AA 4.0 Agglomerates PB1 15.0 10.0 C45AS - 11.0 LAS 6.0 TAS 3.0 Silicate 4.0 Zeolite A 10.0 13.0 MA/AA - 2.0 Citric Acid 4.0 3.0 Spray On Perfume 0.3 0.5 C 45 E 7 4.0 4.0 C 25 E3 2.0 2.0 Dry additives T A E D 4.0 2.0 MA/AA - 3.0 NaSKS-6 - 12.0 Bicarbonate 7.0 5.0 Carbonate 17.0 14.0 PVPVI/PVNO 0.5 0.5 Alcalase 0.5 0.9 Lipase 0.4 0.4 Amylase 0.6 0.6 Cellulase 0.6 0.6 Silicone antifoam 5.0 5.0 Dry additives Sodiurn sulfate 0.0 2.0 Balance (Moisture and Miscellaneous) 100.0 100.0 Density (g/litre) 700 700 CA 0223220~ 1998-03-16 Example 2 The following high density and bleach-cont~ining detergent formulations, according to the present invention were prepared:
C D
Blown Powder Zeolite A 15.0 15.0 Sodium sulfate 0.0 0.0 LAS 3.0 3.0 QAS - 1.5 CEQ 2.0 2.0 DTPMP 0.4 0.4 CMC 0.4 0.4 MA/AA 4.0 2.0 Agglomerates PB1 15.0 15.0 LAS 4.0 4.0 TAS 2.0 1.0 C24E5 2.0 2.0 Silicate 3.0 4.0 Citric Acid 2.0 3.0 Zeolite A 8.0 8.0 Carbonate - 6.0 Magnesium sulphate 0.3 0.4 Spray on Perfume 0.3 0.3 C45E7 2.0 2.0 Dry additives Citrate 5.0 2.0 Bicarbonate Carbonate 16.0 10.0 TAED 6.0 5.0 Polyethylene oxide of MW 5,000,000 - 0.2 Bentonite clay - 10.0 Protease 1.0 1.0 Lipase 0.4 0.4 Amylase 0.6 0.6 Cellulase 0.6 0.6 Silicone antifoam 5.0 5.0 Dry additives Sodium sulfate 0.0 0.0 Balance (Moisture and 100.0 100.0 Miscellaneous) Density (g/litre) 850 850 CA 0223220~ 1998-03-16 Example 3 The following high density detergent formulations, according to the present invention were prepared:
E F
Agglomerate LAS 7.5 PB1 12.0 PB4 - 15.0 C45AS - 14.0 CEQ - 3.5 Zeolite A 15.0 citric acid 1.5 2.0 Carbonate 4.0 MA/AA 4.0 2.0 CMC 0.5 0.5 DTPMP 0.4 0.4 C24E5 5.0 5.0 Spray On Perfume 0.5 0.5 Dry Additives Zeolite - 6.0 HEDP 0.5 0.3 SKS 6 13.0 10.0 Citrate 3.0 1.0 TAED 5.0 7.0 Percarbonate 20.0 20.0 SRP 1 0.3 0.3 Protease 1.4 1.4 Lipase 0.4 0.4 Cellulase 0.6 0.6 Arnylase 0.6 0.6 Silicone antifoarn 5.0 5.0 Brightener 1 0.2 0.2 Brightener 2 0.2 Balance (Moisture and 100 100 Miscellaneous) Density (g/litre) 850 850
Back~round to the Invention There is a trend amongst commercially available granular detergents towards higher 15 bulk densities and towards granular detergent compositions which have a higher content of detergent active ingredients, such as bleach. Such detergents offer greater convenience to the consumer and at the same time reduce the amount of packaging materials which will, ultimately, be disposed of. However, traditional detergentformulations and processes to produce the final detergent powder are not always 20 satisfactory or suitable for these detergents, with higher active ingredient concentration.
Amongst consumers there is also a need for detergents which provide improved bleachable stain removal. Therefore, in the recent past detergents have been 25 developed which contain various types of bleaches, which can be incorporated at high levels.
The (high density) detergents, comprising high levels of bleach and surfactant can lead to poor solubility properties, arising from low rate of dissolution or the 30 formation of gels, and thus to poor dispensing of the product, either from the dispensing drawer of a washing m~rhine, or from a dosing device placed with the laundry inside the m~chine. This poor dispensing is often caused by gelling of particles, which have high levels of surfactant and/ or bleach, upon contact with water. The gel prevents a proportion of the detergent powder from being solubilized 35 in the wash water which reduces the effectiveness of the powder. This is a particular problem at low water pressures and/or at lower washing temperature.
CA 0223220~ 1998-03-16 EP-A-0 639 637 discloses the replacement of perborate bleach with an alkali metal percarbonate to improve the dispensing profile and dissolution rate of a detergent.
Citrate or mixtures of citrate with sulphate or carbonate can be used to coat the percarbonate bleach.
EP-A-0 639 639 contains a similar disclosure in this respect.
Other ways to improve dispensing include the use of an effervescence system. If the detergent contains an effervescence system then the generation of a gas such as carbon dioxide pushes the particles of the d~lelgelll apart, and prevents them from gelling.
The use of effervescence to improve the dispensability of granular materials has been used extensively in ph~ ceutical preparations. The most widely used effervescentsystem in this respect is citric acid in combination with bicarbonate. The use of this simple effervescent system has also been described for improving the dispersibility of pesticidal compositions for controlling water-borne pests, e.g. GB-A-2,184,946.
EP-A-0 534 525 discloses the use of citric acid with a specified particle size range of 350 to 1500 microns.
US -A-5, 114,647 discloses a s~niti.~ing composition comprising granules of alkali metal carbonate and aliphatic carboxylic acid of a particle size of 150 to 2,000microns.
EP-A-0 333 223 discloses a bathing plepal~lion comprising fumaric acid having anaverage particle size of 50-500 microns.
The Applicants have found that one of the specific problems associated with poor30 dispensing of detergent compositions which contain ble~.~hing agents and particularly perborate monohydrate bleach, is that localised high concentrations of bleach form which may contact the fabric and cause spot bleaching of coloured fabrics. Secondly, poorly dispensed surfactants tend to deposit on the fabric and the machine. This can lead to fabric damage. These problems can be encountered 35 especially with detergent compositions comprising high levels of surfactants and perborate, especially perborate (monohydrate). However, these high concentrations are often required for an optimal stain/soil removal and suspension and bleachable stain removal.
The Applicants now have found that this problem can be solved or reduced when an5 acid source is agglomerated with or extruded along with the surfactants, or a part thereof, and the perborate bleach to form an agglomerated or extruded d~lelgent particle. In the detergent comprising this agglomerated or extruded particle, an alkali source should be present, capable of producing a gas when reaction with the acidic source. We have found that agglomerating or extruding of such an acid source with 10 surfactant(s) and bleach, when there is an alkali source present in the detergent composition, improves the solubility and/or dispersion of the surfactant(s) and the perborate bleach in the wash water and elimin~tes or reduces the problems of fabric damage by high concentrate bleach and of solid detergent particles or surfactants rem~ining in the washing m~chine and on washed clothes. It is believed that the acid 15 reacts rapidly with the alkali in the wash water to release the gas. This helps disperse the perborate bleach and the detergent in general surfactants and minimi~e the formation of high concentrations of bleach and of insoluble clumps.
The improved dispensing of the surfactant(s) and the perborate bleach can amount to 20 an overall improved and more efficient performance.
Furthermore, the detergent residues in the dispensing drawer or dispensing device are reduced.
25 All documents cited in the present description are, in relevant part, incorporated herein by reference.
Summary of the Invention 30 According to the present invention there is provided an agglomerate or extruded detergent particle comprising a perborate component, one or more surfactants and an acid source. Optionally other detergent ingredient can be present in the agglomerate or extrudate. The agglomerated or extruded dt;telgent particle can be included in delelgellts comprising an alkali source capable of reacting with the acid source to 35 produce a gas. According to the present invention there is also provided a process for making the agglomerate or extruded detergent particle.
CA 0223220~ 1998-03-16 Detailed Description of the Invention s A~lomerate or extruded particle The agglomerate or extruded detergent particle of the present invention contains one or more surfactants and an acid source and a perborate component, which are described below.
The amount of each component in the agglomerate or extruded detergent particle can vary depending on the application of the particle and on the nature of the finaldetergent composition comprising the particle. For example, when the particle will be used in a detergent composition comprising one or more of the same ingredients as the particle, the level thereof in the particle can be reduced.
The level of surfactant in the particle is preferably from 15% to 95%, more preferably from 25% to 60%, most preferably from 30% to 50% by weight of the particle.
The level of acid source in the particle is preferably from 1% to 40%, more preferably from 3% to 30%, even more preferably from 5% to 25%, most preferably from 7% to 15% by weight of the particle The level of perborate component in the particle is preferably from 10% to 70%, more preferably from 15% to 50%, most preferably from 20% to 40% by weight of the particle.
Preferably, at least one anionic surfactant is present. In a pl~f~lled embodiment a nonionic surfactant and an anionic surfactant are present. In a further preferred embodiment an anionic and a cationic and optionally a nonionic surfactant are present. When a cationic sllrf~t~nt is present, preferably a silicate or alumino silicate 35 co.~ ing material is present.
CA 0223220~ 1998-03-16 Preferably, magnesium sulphate is present in the particle, preferably at a level of from 0.1% to 8%, more preferably of from 0.2% to 5%, most preferably from 0.3%
to 3% by weight of the particle.
5 Preferably, the particle does not comprise a bleach activator and/ or crystalline layered silicate.
The agglomerate or extruded particle can optionally comprise additional detergent ingredients. Preferred optional ingredients in the particle can be builders (alumino 10 silicates, polymeric carboxylates), an alkali source, bleach activators and bleach catalysts.
Surfactant 15 The level of surfactant in the particle is preferably from 15% to 95%, more preferably from 25% to 60%, most preferably from 30% to 50% by weight of the particle.
When the particle is comprised in a detergent composition, the total level of 20 surfactant in the d~lergellt composition is preferably of from 1% to 90%, preferably 3% to 70%, more preferably 5% to 40%, even more preferably 10% to 30%, most preferably 12% to 25% by weight ofthe detergent composition.
The surfactant in the agglomerate or extruded particle is selected from anionic,25 nonionic and cationic surfactants and mixtures thereof.
Optionally, ampholytic, amphoteric and zwitterionic surfactants can be present in the particle.
30 A typical listing of anionic, nonionic, ampholytic, and zwitterionic classes, and species of these surfactants, is given in U.S.P. 3,929,678 issued to T ~lghlin and Heuring on December 30, 1975. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A list of suitable cationic surfactants is given in U.S.P. 4,259,217 issued to Murphy on March 35 31, 1981.
CA 0223220~ 1998-03-16 Anionic surfactant The agglomerated or extruded detergent particle in accordance with the present invention preferably comprise one or more anionic surfactants. Essentially any 5 anionic surfactants useful for detersive purposes can be comprised in the detergent composition. These can include salts (including, for example, sodium, potassium,ammonium, and substituted ammonium salts such as mono- di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants.
Anionic sulfate surfactants are preferred.
The level of anionic surfactant is preferably from 10% to 95%, more preferably from 20% to 60%, most preferably from 25% to 50% by weight of the particle.
In detergent compositions, comprising the particle, the total level of anionic surfactant is preferably from 2% to 40%, more preferably from 4% to 30%, even more preferably from 5% to 25%, most preferably from 6% to 15% by weight ofthe composltlon.
Other anionic surfactants include the isethionates such as the acyl isethionates, N-20 acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C12-C1 8 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C6-C 14 diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated 25 resin acids present in or derived from tallow oil.
Anionic sulfate surfactant Anionic sulfate surf~t~nt.c suitable for use herein include the linear and branched 30 primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol snlf~tes, alkyl phenol ethylene oxide ether slllf~tes, the Cs-C17 acyl-N-(C1-C4 alkyl) and -N-(C1-C2 hydroxyalkyl) gluc~mine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
CA 0223220~ 1998-03-16 Alkyl sulfate surfactants are preferably selected from the linear and branched primary C 1 o-C 18 alkyl sulfates, more preferably the C1 1 -C 15 branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates.
Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C1o-C1g alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C 1 1 -C l 8, most preferably C 1 1 -C 1 5 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.
A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.
15 Anionic sulfonate surfactant Anionic sulfonate surfactants suitable for use herein include the salts of Cs-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl 20 glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
Anionic carboxylate surfactant 25 Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.
Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH20)X
30 CH2COO-M+ wherein R is a C6 to C 1 8 alkyl group, x ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 % and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHRl-CHR2-O)-R3 wherein R is a C6 to C 18 alkyl group, x is from 1 to 25, R1 and R2 are selected from the group 35 consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of CA 0223220~ 1998-03-16 hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbonatoms, and mixtures thereof.
Suitable soap surfactants include the secondary soap surfactants which contain a5 carboxyl unit connected to a secondary carbon. Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl- 1 -undecanoic acid, 2-ethyl-1 -decanoic acid, 2-propyl-l-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps may also be included as suds suppressors.
Alkali metal sarcosinate surfactant Other suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON
(Rl) CH2 COOM, wherein R is a Cs-C17 linear or branched alkyl or alkenyl group, 15 R1 is a C1-C4 alkyl group and M is an alkali metal ion. Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.
Cationic surfactants 20 Another pr~r~lled surfactant of the invention is one or more cationic surfactants.
Suitable cationic surf~ct~nt~ include the qll~tern~ry ammonium surfactants selected from mono C6-C16, preferably C6-C1o N-alkyl or alkenyl ammonium surfactants wherein the renl~ining N positions are substituted by methyl, hydroxyethyl or hydroxy~ropyl groups. Another pier~ll~ cationic surfactant is an C6-C 18 alkyl or 25 alkenyl ester of an q~l~tçrn~ry ammonium alcohol, such as qll~t~?rn~ry choline esters.
The level of cationic surfactant is preferably from 1% to 20%, more preferably from 2% to 15%, most preferably from 4% to 10% by weight ofthe particle.
30 In detergent compositions, comprising the particle, the level of cationic surfactant is preferably from 0.2% to 20%, more preferably from 0.5% to 15%, even more preferably from 1% to 10%, most preferably from 1% to 5% by weight ofthe composltlon.
CA 0223220~ 1998-03-16 Nonionic surfactant The detergent composition of the present invention preferably contains a nonionic surfactant. Essentially any nonionic surfactant can be used herein.
The level of nonionic surfactant is preferably from 5% to 60%, more preferably from 10% to 45%, most preferably from 15% to 35% by weight ofthe particle.
In detergent compositions, comprising the particle, the level of nonionic surfactant is preferably from 1% to 30%, more preferably from 2% to 25%, even more preferably from 3% to 15%, most preferably from 4% to 12% by weight ofthe composition.
Alkoxylated nonionic surfactant Essentially any alkoxylated nonionic surfactants are suitable herein. The ethoxylated and propoxylated nonionic surfactants are preferred.
Preferred alkoxylated surfactants can be selected from the classes of the nonionic cond~n~tes of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene ~ mine adducts.
Nonionic alkoxylated alcohol surfactant The con-lPnc~tion products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are suitable for use herein.
The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group cont~ining from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
Nonionic polyhydroxy fatty acid amide surfactant Polyhydroxy fatty acid amides suitable for use herein are those having the structural formulaR2CONR1Z wherein: R1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C 1 -C4 alkyl, more CA 0223220~ 1998-03-16 , preferably Cl or C2 alkyl, most preferably Cl alkyl (i.e., methyl); and R2 is a Cs-C3 1 hydrocarbyl, preferably straight-chain Cs-C 19 alkyl or alkenyl, more preferably straight-chain Cg-C 17 alkyl or alkenyl, most preferably straight-chain Cl 1 -C 17 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear 5 hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.
10 Nonionic fatty acid amide surfactant Suitable fatty acid amide surfactants include those having the formula: R6CoN(R7)2 wherein R6 is an alkyl group cont~inin~ from 7 to 21, preferably from 9 to 17 carbon atoms and each R7 is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and -(C2H4O)XH, where x is in the range of from 1 to 3.
Nonionic alkylpolysaccharide surfactant Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group cont~ining from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group cont~ining from 1.3 to 10 saccharide units.
Preferred alkylpolyglycosides have the formula R20(CnH2nO)t(glycosyl)x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The glycosyl is preferably derived from glucose.
CA 0223220~ 1998-03-16 Optional surfactants Amphoteric surfactant 5 Optional amphoteric surfactants for use in the particle or detergent compositions, comprising the particle, include the amine oxide surfactants and the alkyl amphocarboxylic acids.
Suitable amine oxides include those compounds having the formula R3(oR4)XN0(R5)2 wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, cont~ining from 8 to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group C~ g from 2 to 3 carbon atoms, or mixtures thereof, x is from 0 to 5, preferably from 0 to 3; and each R5 is an alkyl or hydroxyalkyl group cont~ining from 1 to 3, or a polyethylene oxide 15 group cont~inin~ from 1 to 3 ethylene oxide groups. Preferred are Clo-Clg alkyl dimethylamine oxide, and Clo 1 8 acylamido alkyl dimethylamine oxide.
A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Conc.
manufactured by Miranol, Inc., Dayton, NJ.
Zwitterionic surfactant Optionally, zwitterionic surfactants can be incorporated into the particle or detergent compositions comprising the particle. These s~ ct~nt~ can be broadly described as 25 derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary ~mines, or derivatives of quaternary ammonium, q~-~t~rn~ry phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
30 Suitable betaines are those compounds having the formula R(R')2N+R2COO-wherein R is a C6-C1g hydrocarbyl group, each Rl is typically C1-C3 alkyl, and R2 is a Cl-Cs hydrocarbyl group. Preferred betaines are C12 18 dimethyl-ammonio hexanoate and the C10-l8 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.
CA 0223220~ 1998-03-16 Acid source In accordance with the present invention, an acid source, or source of acidity, is present in the agglomerate or extruded detergent particle. When comprised in a 5 detergent composition, the detergent composition contains an alkali source, capable of reacting with the acid source to produce a gas. Optionally, the alkali source or part thereof can be comprised in the particle.
The level of the acid source in the particle is preferably from 1% to 40%, more preferably from 3% to 30%, even more preferably from 5% to 25%, most preferably from 7% to 15% by weight of the particle.
In detergent compositions comprising the particle, the level of the source of acidity is preferably present of from 0.1% to 50%, more preferably from 0.5% to 25%, even more preferably from 1% to 12%, most preferably from 1% to 7% weight of the composltlon.
Preferably, 80% or more of the acid source has a particle size in the range of from about 150 microns to about 710 microns, with at least about 37% by weight of the20 acid source having a particle size of about 350 microns or less. In a plef~lled embodiment 100% of the acid source has a particle size of about 710 microns or less.
Alternatively, greater than about 38%, more preferably 38.7%, of the particulate acid source has a particle size of about 350 microns or less.
25 The particle size of the acid source is calculated by sieving a sample of the source of acidity on a series of Tyler sieves. For example, a Tyler sieve mesh 100 corresponds to an ap~ ule size of 150 microns. The weight fractions thereby obtained are plotted against the aperture size of the sieves.
30 The acid source may be any suitable organic, mineral or inorganic acid, or a derivative thereof, or a mixture thereof. The acid source may be a mono-, bi- or tri-protonic acid. Preferred derivatives include a salt or ester of the acid. The source of acidity is preferably non-hygroscopic, which can improve storage stability. However, monohydrates acids can also be useful herein. Organic acids and their derivatives are 35 preferred. The acid is preferably water-soluble. Suitable acids include citric, glutaric, CA 0223220~ 1998-03-16 succinic or adipic acid, monosodium phosphate, sodium hydrogen sulfate, boric acid, or a salt or an ester thereof. Citric acid is especially preferred.
5 Perborate component Another essential ingredient of the agglomerate or extruded detergent particle of the present invention is a perborate component, which is capable of bleaching.
10 The level of perborate component in the particle is preferably from 10% to 70%, more preferably from 15% to 50%, most preferably from 20% to 40% by weight of the particle.
In detergent compositions comprising the particle, the perborate is preferably present at a level of from 1% to 40% by weight, more preferably from 6% to 25% by weight, most preferably from 13% to 20% by weight of the compositions.
The perborate is preferably in the form of a salt, normally in the form of the alkali metal, preferably sodium salt.
The perborate bleach is preferably sodium perborate in the form of the monohydrate or tetrahydrate, which can be represented respectively with the nominal formula NaBO2H2O2 and NaB~2H2~2 3H2o 25 The perborate bleach may be included as the crystalline solid without additional protection. However, ple~lled executions of certain granular compositions utilize a coated form of the perborate bleach which provides better storage stability for the perhydrate salt in the granular product. Suitable coatings comprise inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic 30 materials such as waxes, oils, or fatty soaps.
Source of Alkali In accordance with the present invention, when the agglomerate or extruded 35 detergent particle is present in a detergent composition, an alkali source is generally present in the detergent composition such that it has the capacity to react with the CA 0223220~ 1998-03-16 acid source to produce a gas. Preferably this gas is carbon dioxide, and therefore the alkali is a carbonate, or a suitable derivative thereof.
Optionally, the alkali source, or part thereof can be present in the particle.
The detergent composition comprising the particle of the present invention, preferably contains from about 2% to about 75%, preferably from about 5% to about 60%, most preferably from about 10% to about 30% by weight of the alkali source.When the alkali source is present in the particle, the agglomerate or extrudate preferably contains from about 5% to about 60%, more preferably from 10% to 50%,most preferably from 15% to 35% of the alkali source.
In a preferred embodiment, the alkali source is a carbonate. Examples of pl~r~ dcarbonates are the ~lk~line earth and alkali metal carbonates, including sodium carbonate, bicarbonate and sesqui-carbonate and any mixtures thereof with ultra-fine calcium carbonate such as are disclosed in German Patent Application No. 2,321,001 published on November 15, 1973. Alkali metal percarbonate salts may also be included in the detergent compositions and are also suitable sources of carbonate species and are described below in more detail.
Other suitable sources will be known to those skilled in the art.
The alkali source may also comprise other components, such as a silicate. Suitable silicates include the water soluble sodium silicates with an SiO2: Na2O ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.0 being preferred, and 2.0 ratio being most preferred. The silicates may be in the form of either the anhydrous salt or a hydrated salt. Sodium silicate with an SiO2: Na20 ratio of 2.0 is the most pl~;r~lled silicate.
Alkali metal persilicates are also suitable sources of silicate herein.
Process for makin~ of the a~lomerate particle The agglomerate detergent particle can be prepared via a process comprising the steps of:
i) allmixing one or more detergent surfactants, the perborate component and an acid source and optionally other detergent ingredientsto form a mixture; and CA 0223220~ 1998-03-16 ii) agglomerating the mixture to form agglomerated particles.
Typically, such a process involves mixing an effective amount of powder, including 5 the acid source, with a high active surfactant paste in one or more agglomerators such as a pan agglomerator, a Z-blade mixer or more preferably in-line mixers, preferably two, such as those m~nllf~tllred by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, and Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1, Elsenerstrasse 7-9, Postfach 2050, Germany. Preferably a high shear10 mixer is used, such as a Lodige CB (Trade Name). Most preferably, a high shear mixer is used in combination with a low shear mixer, such as a Lodige CB (Trade Name) and a Lodige KM (Trade name) or Schugi KM (Trade Name). Optionally, only one or more low shear mixer are used. Preferably, the agglomerates are thereafter dried and/ or cooled.
An other agglomeration process involves mixing of various components of the final agglomrate in different stages, using an fluidised bed. For example, a preferredparticle in accord with the present invention can be agglomerated by addition, preferably by spraying on, of nonionic, anionic surf~ct~nt~ and optionally a wax, or 20 mixtures thereof, to the acid source in powdered form and other optional ingredients.
Then, additional components, including the perborate bleach and optinally the alkali source or part thereof, can be added and agglomerated in one or more stages, thus forming the final agglomerate particle.
25 Preferably, no bleach activator and/ or crystalline layered silicate is added to the agglomerate mix in the agglomeration process for making the particle of the invention.
The agglomerate particles may take the form of flakes, prills, marumes, noodles,30 ribbons, but preferably take the form of granules. A plef~lled way to process the particles is by agglomerating powders (e.g. aluminosilicate, carbonate) with high active surfactant pastes and to control the particle size of the resulting agglomerates within specified limits. Typical particle sizes are from 0.10 mm to 5.0 mm in diameter, preferably from 0.25 mm to 3.0 mm in diameter, most preferably from 0.40 35 mm to 1.00 mm in diameter.
CA 0223220~ 1998-03-16 A high active surfactant paste comprising a mix of, typically, from 50% by weight to 95% by weight, preferably 70% by weight to 85% by weight of surfactant, and optionally it can contain an appropriate acid source. The paste may be pumped into the agglomerator at a temperature high enough to m~int~in a pumpable viscosity, but 5 low enough to avoid degradation of the anionic surfactants used. An operating telllpcldlllre of the paste of 50~C to 80~C is typical. Such pastes and methods for making and processing such pastes is for example described in WO 93/03128.
In an especially preferred embodiment of the present invention, the detergent 10 composition has a density of greater than about 600 g/l and is in the form of powder or a granulate.
Process for makin~ the extruded particle 15 Extruded particles can generally be prepared by mixing the various components, optionally addition of powdered components and/or slip additives, forcing the obtained mixture by pressure through the extruder holes of the required diameter or less, cutting of the extruded paste into extrudates (granules) of the required length and rounding the extrudates. WO 91/13678 and WO 91/02047 describe such 20 processes.
In more detail the extruded particles can be made as follows. The detergent ingredients can be mixed into one paste. Preferably, the various detergent components are pre-mixed in dirr~lelll pastes, preferably two, whereby the acid 25 source preferably is present in a dirr~,le.l~ pre-mixed past than the alkali source if present in the particle, especially when the alkaline source is a carbonate or bicarbonate.
In a highly plefcll~d embo~liment one pre-mixed paste comprises the perborate 30 component and part of the surfactant, preferably the anionic surfactant if present, and additional components such as zeolite and cationic surfactant, and one pre-mixedpaste comprises the acid source and part of the surfactant, preferably the nonionic surfactant. The premixed pastes will then be mixed to form one paste.
35 Optionally, water and additional detergent components, such as slip additives, additional bleach, enzymes, optionally bleach activators, stabilisers and soap can be CA 0223220~ 1998-03-16 added to the pre-mixed paste or pastes or to the paste as a whole, simultaneously with or shortly after the mixing process has started.
Preferably the paste obtained is coated with a slip material prior to or simultaneously 5 with the introduction of the paste in the extruder. A variety of compounds are known to be useful herein as slip additives. Preferred slip additives are those compounds which also have a secondary detergent function, such as certain anionic and nonionic surfactants, polymeric polycarboxylates, polyvinyl alcohols.
10 Under pressure (20 bar or more) the paste or coated paste is then passed through the holes (of the extruder) of the required diameter or less, whereafter the extruded granules are cut in to granules of the required length (about 0.1 mm to 2.0 mm, preferably about 0.4 mm to 1.0 mm).
Typical particle diameter sizes (width) are from 0.10 mm to 5.0 mm, preferably from 0.25 mm to 3.0mm, most preferably from 1.00 mm to 2.50.
The viscosity of the paste should be controlled to avoid caçking of the paste in the extruder or during mixing and to avoid the paste from blocking the extruder. By 20 constant ples~ule, the viscosity is best controlled by heating and cooling the paste and/ or the extruder.
Optionally, the obtained extrudates are rounded, to obtain round or spherical particles.
Preferably, the thus obtained particles are dusted with a powder, preferably zeolite, and dried, to form equally shaped granules, and to avoid agglomeration of the granules.
30 Additional ingredients The agglomerate or extruded detergent particle and/ or the detelgell~ compositions, comprising the particle of the invention, may also contain additional ingredients or components. The precise nature of these additional ingredients, and levels of CA 0223220~ 1998-03-16 .
incorporation thereof will depend on the physical form of the final composition, and the precise nature of the washing operation for which it is to be used.
The detergent particle preferably comprises as an additional ingredient one or more S builders, preferably alumino silicates and/ or organic polycarboxylate polymers, alkali sources, bleach activators or bleach catalysts, or mixtures thereof.
The detergent compositions, comprising the particle of the invention, preferablycontain one or more additional detergent components selected from surfactants as10 described above, additional acid sources, additional bleaches, builders, organic polymeric compounds, enzymes, suds suppressors, lime soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors.
Water-soluble builder compound The particle and/ or the detergent compositions of the present invention can contain a water-soluble builder compound, typically present in deLelg~ compositions at a level of from 1% to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% by weight of the composition.
Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, phosphates, 25 and mixtures of any of the foregoing.
The carboxylate or polycarboxylate builder can be monomeric or oligomeric in type although monomeric polycarboxylates are generally plere,~ed for reasons of cost and performance.
Suitable carboxylates cont~inin~ one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates cont~ining two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid 35 and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.
Polycarboxylates Co"t~ il-g three carboxy groups include, in particular, water-CA 0223220~ 1998-03-16 .
soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in British Patent No. 1,389,732, and aminosuccinatesdescribed in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No.
1,387,447.
Polycarboxylates cont~ining four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates cont~ining sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000. Preferred polycarboxylates are hydroxycarboxylates cont~ining up to three carboxy groups per molecule, more particularly citrates.
Borate builders, as well as builders cont~ining borate-forming materials that can produce borate under detergent storage or wash conditions are useful water-soluble builders herein.
Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.
Partially soluble or insoluble builder compound The particle and/ or the detergent compositions of the present invention may contain a partially soluble or insoluble builder compound, typically present in the detergent composition at a level of from 1% to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% weight of the composition.
In the particle, the partially soluble or insoluble builder compound is preferably present at a level of from 5% to 85% by weight, preferably from 15% to 60% by weight, most preferably from 20% to 50% weight of the particle.
CA 0223220~ 1998-03-16 Examples of largely water insoluble builders include the sodium aluminosilicates.
Suitable aluminosilicate zeolites have the unit cell formula Naz[(AlO2)z(SiO2)y].
xH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.
The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the design~tions Zeolite A, Zeolite B, Zeolite P, Zeolite X,Zeolite HS and mixtures thereof. Zeolite A has the formula Na 12 [AlO2) 12 (SiO2)l2] xH2O
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na86 [(Alo2)g6(sio2)lo6]- 276 H2O.
Preferably, the particle of the invention does not comprise a crystalline layered silicate. However, pl~fe~.~d crystalline layered silicates for use in the detegrent compositions herein have the general formula NaMSixO2x+l YH2o wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their p.~palalion are disclosed in DE-A-3417649 and DE-30 A-3742043. Herein, x in the general formula above preferably has a value of 2, 3 or 4 and is preferably 2. The most preferred material is ~-Na2Si20s, available fromHoechst AG as NaSKS-6.
Additional perhydrate bleaches CA 0223220~ 1998-03-16 In addition to the perborate bleach, metal percarbonates, particularly sodium percarbonate is an optional perhydrate which can be incorporated into the particle or detergent composition of the invention. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2CO3.3H2O2, and is available 5 commercially as a crystalline solid.
Potassium peroxymonopersulfate, sodium per is another optional inorganic perhydrate salt of use in the detergent compositions herein.
10 Or~anic peroxYacid bleachin~ system A pl~el~lled feature of detergent compositions of the invention is an organic peroxyacid bleaching system. In one ~efe,l~d execution the bleachin~ system contains a hydrogen peroxide source and an organic peroxyacid bleach precursor 15 compound. The production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches, such as the perborate bleach of the claimed invention. In an alternative p~ef~ d execution a plefollned organic peroxyacid is incorporated directly into the composition. Compositions cont~inin~
20 mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.
Peroxyacid bleach precursor 25 Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be represented as O
X-C -L
where L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is o X-C-OOH
CA 0223220~ 1998-03-16 Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 20% by weight, more preferably from 1% to 15% by weight, most preferably from 1.5% to 10% by weight of the detergent compositions.
Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, which precursors can be selected from a wide range of classes.
Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798,l 147871, 2143231 and EP-A-0170386.
Leaving ~roups 15 The leaving group, hereinafter L group, must be sufficiently reactive for theperhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle).
However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.
25 Preferred L groups are selected from the group consisting of:
--O~ ~~Y and --O~
IR3 ~ ' R3 Y
CA 0223220~ 1998-03-16 R3 r -O--CH=C--CH=CH2 --O--CH=C--CH=CH2 1~l Y 1~l -O--C--R1 --N/ ~NR4 --N /NR4 --O--C=CHR4 , and IN i--CH--R4 R3 o and mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group cont~ining from 1 to 14 carbon atoms, R3 is an alkyl chain cont~ining from 1 to 8 carbon atoms, R4 is H or R3, and Y is H or a solubilizing group. Any of R1, R3 and R4 may be substituted by essentially any functional group including, for example alkyl, 10 hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups.
The preferred solubilizing groups are -SO3 M, -CO2 M, -SO4 M, -N (R3)4X
and o<--N(R3)3 and most preferably -SO3-M+ and -CO2-M+ wherein R3 is an alkyl 15 chain co~ il-g from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.
Alkyl percarboxylic acid bleach precursors Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis. Preferred precursors of this type provide peracetic acid on 25 perhydrolysis.
CA 0223220~ 1998-03-16 Preferred alkyl percarboxylic precursor compounds of the imide type include the N-,N,NlNl tetra acetylated alkylene ~ mines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is 5 particularly preferred. The TAED is preferably not present in the agglomeratedparticle of the present invention, but preferably present in the detergent composition, comprising the particle.
Other p.efel.~d alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl 10 hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
Amide substituted alkyl peroxyacid precursors 15 Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae:
R1~C N~R2 C L R1 N~C~R2- C~L
, O R5 0 or R5 0 0 20 wherein Rl is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene group cont~ining from 1 to 14 carbon atoms, and R5 is H or an alkyl group cont~ining 1 to 10 carbon atoms and L can be essentially any leaving group. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
Perbenzoic acid precursor Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
Suitable O-acylated perbenzoic acid precursor compounds include the substituted and 30 unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products ofsorbitol, glucose, and all saccharides with benzoylating agents, and those of the imide type including N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas. Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole. Other useful N-acyl CA 0223220~ 1998-03-16 group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
Cationic peroxyacid precursors s Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.
Typically, cationic peroxyacid precursors are formed by substituting the peroxyacid 10 part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkyl ammmonium group, preferably an ethyl or methyl ammonium group. Cationic peroxyacid precursors are typically present in the solid detergent compositions as a salt with a suitable anion, such as a halide ion.
The peroxyacid precursor compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof, precursor compound as described hereinbefore. Alternatively, the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid 20 precursor as described hereinafter.
Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015;
4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,382,594;
EP 475,512, 458,396 and 284,292; and in JP 87-318,332.
Examples of pler~ d cationic peroxyacid precursors are described in UK Patent Application No. 9407944.9 and US Patent Application Nos. 08/298903, 08/298650, 08/298904 and 08i298906.
30 Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium 35 methylene alkyl caprolactams.
CA 0223220~ 1998-03-16 Benzoxazin organic peroxyacid precursors Also suitable are precursor compounds of the benzoxazin-type, as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the forrnula:
col [~N"C R1 wherein R1 is H, alkyl, alkaryl, aryl, or arylalkyl.
10 Preformed organic peroxyacid The organic peroxyacid bleaching system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid, typically at a level of from 1% to 15% by weight, more 15 preferably from 1% to 10% by weight of the composition.
A preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae:
O R5 o or wherein Rl is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is an alkylene, arylene, and alkarylene group cont~inin~ from 1 to 14 carbon atoms, and 25 RS is H or an alkyl, aryl, or alkaryl group co~ il-g 1 to 10 carbon atoms. Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.
CA 0223220~ 1998-03-16 , Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-phthaloylaminoperoxicaproic acid are also suitable herein.
Bleach catalyst The particle and/ or the compositions optionally contain a transition metal cont~ining bleach catalyst. One suitable type of bleach catalyst is a catalyst system comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron orm~ng~nese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylene~i~minetetraacetic acid, ethylene~i~minetetra(methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S. Pat. 4,430,243.
Other types of bleach catalysts include the m~ng~n~se-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts include MnIV2(u-O)3(1,4,7-trimethyl- 1,4,7-triazacyclononane)2-(PF6)2, MnIII2(u-O) 1 (u-OAc)2(1,4,7-trimethyl- 1,4,7-triazacyclononane)2-(ClO4)2, MnIV4(u-O)6(1,4,7-triazacyclononane)4-(ClO4)2, MnIIIMnIV4(u-O) 1 (u-OAc)2 (1,4,7-trimethyl-1,4,7-triazacyclononane)2-(ClO4)3, and mixtures thereof. Others are described in European patent application publication no. 549,272. Other ligands suitable for use herein include 1,5,9-trimethyl- 1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl- 1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and mixtures thereof.
For examples of suitable bleach catalysts see U.S. Pat. 4,246,612 and U.S. Pat.
5,227,084. See also U.S. Pat. 5,194,416 which teaches mononuclear m~ng~nese (IV)complexes such as Mn(1,4,7-trimethyl-1,4,7-tri~7~cyclononane)(OCH3)3 (PF6). Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is a water-soluble complex of m~ng~nese (III), and/or (IV) with a ligand which is a non-carboxylatepolyhydroxy compound having at least three consecutive C-OH groups. Other examples include binuclear Mn complexed with tetra-N-dentate and bi-N-dentate lig~n-l~, including N4MnIII(u-0)2MnIVN4)+and [Bipy2MnIII(u-0)2MnIVbipy2]-(C104)3.
CA 0223220~ 1998-03-16 Further suitable bleach catalysts are described, for example, in European patentapplication No. 408,131 (cobalt complex catalysts), European patent applications, publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S. 4,728,455 (m~ng~nese/multidentate ligand catalyst), U.S. 4,711,748 and European patent application, publication no. 224,952, (absorbed m~ng~nese on aluminosilicate catalyst), U.S. 4,601,845 (aluminosilicate support with m~ng~nese and zinc or m~gnesium salt), U.S. 4,626,373 (m~n~nese/ligand catalyst), U.S. 4,119,557 (ferric complex catalyst), German Pat. specification 2,054,019 (cobalt chelant catalyst)10 C~n~ n 866,191 (transition metal-cont~inin~. salts), U.S. 4,430,243 (chelants with m~ng~nese cations and non-catalytic metal cations), and U.S. 4,728,455 (m~ng~nPse gluconate catalysts).
Heavy metal ion sequestrant The particle and or the detergent compositions, comprising the particle of the invention preferably contain as an optional component a heavy metal ion sequestrant.
By heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and 20 magnesium chelation capacity, but pr~rerelltially they show selectivity to binding heavy metal ions such as iron, m~n~nese and copper.
Heavy metal ion sequestrants are generally present at a level of from 0.005% to 20%, preferably from 0.1% to 10%, more preferably from 0.25% to 7.5% and most 25 preferably from 0.5% to 5% by weight of the compositions.
Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy disphosphonates and nitrilo trimethylene phosphonates.
Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene ~ mine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate.
35 Other suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylene~i~minotetracetic acid, CA 0223220~ 1998-03-16 ethylenetriamine pentacetic acid, ethylene~i~rnine disuccinic acid, ethylene~ mine diglutaric acid, 2-hydroxypropylene~ mine disuccinic acid or any salts thereof Especially prer~lled is ethylene.li~-nine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or5 mixtures thereof.
Other suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133. The iminodiacetic acid-N-2-10 hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein. The ,B-alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants described in EP-A-509,382 are also suitable.
EP-A-476,257 describes suitable amino based sequestrants. EP-A-510,331 describessuitable sequestrants derived from collagen, keratin or casein. EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid are also suitable. Glycinamide-N,N'-20 disuccinic acid (GADS), ethylenetli~mine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylene~ min~-N-N'-disuccinic acid (HPDDS) are also suitable.
EnzYme 25 Another plef~lled ingredient useful in the detergent compositions, comprising the particle, is one or more additional enzymes. Optionally, the enzymes or part thereof cam be present in the agglomerated or extruded particle of the invention.
Preferred additional enzymatic materials include the commercially available lipases, 30 cutinases, amylases, neutral and ~lk~line proteases, esterases, cellulases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions.
Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
Preferred commercially available protease enzymes include those sold under the 35 tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denrnark), those sold under the tr~dçn~rne Maxatase, Maxacal and Maxapem CA 0223220~ 1998-03-16 -by Gist-Brocades, those sold by Genencor International, and those sold under thetr~clen~me Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001 % to 4% active enzyme by weight of the composition.
Preferred amylases include, for example, a-amylases obtained from a special strain of B licheniformis, described in more detail in GB-1,269,839 (Novo). Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename 10 Termamyl and BAN by Novo Industries A/S. Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight of the composition.
Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001% to 2% by weight, preferably 0.001% to 1% by weight, most preferably from0.001% to 0.5% by weight ofthe compositions.
The lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp.
20 including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase fromchemically or genetically modified mutants of these strains are also useful herein. A
preferred lipase is derived from Pseudomonas pseudoalcali~enes. which is described in Granted European Patent, EP-B-0218272.
25 Another plefelled lipase herein is obtained by cloning the gene from Humicolal~nu~inosa and ~ressing the gene in Asper~illus oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available fromNovo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.
Or~anic polymeric compound Organic polymeric compounds are preferred additional components of the particle and/ or the d~lel~ ll compositions, comprising the particle in accord with the 35 invention, and are preferably present as components of any particulate components where they may act such as to bind the particulate component together. By organic CA 0223220~ 1998-03-16 polymeric compound it is meant herein essentially any polymeric organic compoundcommonly used as dispersants, and anti-redeposition and soil suspension agents in dete~gent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein.
Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.1 % to 30%, preferably from 0.5% to 15%, most preferably from I % to 10% by weight of the compositions.
10 Examples of organic polymeric compounds include the water soluble organic homo-or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers ofthe lattertype are disclosed in GB-A-1,596,756.
Examples of such salts are polyacrylates of MWt 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 100,000, especially 40,000 to 80,000.
The polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
Terpolymers cont~ining monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.
Other organic polymeric compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.
Further useful organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.
Another organic compound, which is a preferred clay dispersant/ anti-redeposition agent, for use herein, can be the ethoxylated cationic monoamines and ~i~mines of the formula:
CA 0223220~ 1998-03-16 X i OCH2CH2) N+ CH2---CH2~CH2)a b N CH2 2 (CH2CH20 -)~ X (CH2CH20 ~ X
wherein X is a nonionic group selected from the group consisting of H, C1-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof, a is from 0 to 20, preferably from 0 to 4 (e.g. ethylene, propylene, hexamethylene) b is 1 or 0; for cationic mono~mines (b=0), n is at least 16, with a typical range of from 20 to 35; for cationic diamines (b=1), n is at least about 12 with a typical range of from about 12 to about 42.
Other di~l~cr~a~ / anti-redeposition agents for use herein are described in EP-B-10 011965 and US 4,659,802 and US 4,664,848.
Suds suppressing system The detergent compositions, when formulated for use in m~hine washing 15 compositions, preferably comprise a suds suppressing system present at a level of from 0.01% to 15%, preferably from 0.05% to 10%, most preferably from 0.1% to 5% by weight of the composition.
Suitable suds suppressing systems for use herein may comprise essentially any 20 known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds.
By antifoam compound it is meant herein any compound or mi~lulcs of compounds which act such as to depress the foaming or sudsing produced by a solution of a 25 detergent composition, particularly in the presence of agitation of that solution.
Particularly prcf~llcd antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica 30 component. The term "silicone" as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types. Preferred silicone CA 0223220~ 1998-03-16 antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.
Other suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and 10 alkanolammonium salts.
Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C 1 g-C40 ketones (e.g. stearone) N-alkylated amino triazines such as tri- to 15 hexa-alkylmel~mine~ or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine cont~ining 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.
A preferred suds suppressing system comprises (a) antifoam compound, preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination (i) polydimethyl siloxane, at a level of from 50% to 99%, preferably 75%
to 95% by weight of the silicone antifoam compound; and (ii) silica, at a level of from 1% to 50%, preferably 5% to 25% by weight of the silicone/silica antifoam compound;
wherein said silicalsilicone antifoam compound is incorporated at a level of from 5%
to 50%, preferably 10% to 40% by weight;
35 (b) a dispersant compound, most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide CA 0223220~ 1998-03-16 -to propylene oxide ratio of from 1 :0.9 to 1: 1.1, at a level of from 0.5% to 10%, preferably 1 % to 10% by weight; a particularly preferred silicone glycol rake copolymer of this type is DCO544, commercially available from DOW
Corning under the tradename DCO544;
s (c) an inert carrier fluid compound, most preferably comprising a C 16-c 18 ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to 70%, by weight;
A highly plerell~d particulate suds su~plessing system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier m~teri~l having a melting point in the range 50~C to 85~C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain cont~ining from 12 to 20 carbon atoms. EP-A-0210721 discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid oralcohol having a carbon chain cont~ining from 12 to 20 carbon atoms, or a mixture thereof, with a melting point of from 45~C to 80~C.
Clay softening system The particle and/ or the detergent compositions may contain a clay softening system comprising a clay mineral compound and optionally a clay flocculating agent.
The clay mineral compound is preferably a smectite clay compound. Smectite claysare disclosed in the US Patents Nos. 3,862,058, 3,948,790, 3,954,632 and 4,062,647.
European Patents Nos. EP-A-299,575 and EP-A-313,146 in the name of the Procter and Gamble Company describe suitable organic polymeric clay flocculating agents.
Polymeric dye transfer inhibitin~ a~ents The particle, but preferably the detergent compositions may also comprise from 0.01% to 10 %, preferably from 0.05% to 0.5% by weight of polymeric dye transferinhibiting agents.
CA 0223220~ 1998-03-16 The polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof.
S a) Polyamine N-oxide polymers Polyamine N-oxide polymers suitable for use herein contain units having the following structure formula:
(I) Ax R
wherein P is a polymerisable unit, and A is NC, CO, C, -O-, -S-, -N-; x is O or1;
R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-O group can be attached orwherein the nitrogen of the N-O group is part of these groups.
20 The N-O group can be represented by the following general structures:
o o (R1) X-N-(R2) (R3)z or N-(R1 )x 25 wherein R1, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group forms CA 0223220~ 1998-03-16 part of these groups. The N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic,alicyclic or heterocyclic groups. One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline,10 acridine and derivatives thereof.
Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O groupis attached to the polymerisable unit. A pl~rt;,led class of these polyamine N-oxides comprises the polyamine N-oxides having the general formula (I) wherein R is an 15 aromatic,heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said. R group. Examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
20 The polyamine N-oxides can be obtained in almost any degree of polymerisation.
The degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power. Typically, the average molecular weight is within the range of 500 to 1000,000.
25 b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole Suitable herein are coploymers of N-vinylimidazole and N-vinylpyrrolidone havingan average molecular weight range of from 5,000 to 50,000. The plefe,~ed copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 30 0.2.
c) Polyvinylpyrrolidone The delelgellt compositions herein may also utilize polyvinylpyrrolidone ("PVP")35 having an average molecular weight of from 2,500 to 400,000. Suitable polyvinylpyrrolidones are commercially valuable from ISP Corporation, New York, CA 0223220~ 1998-03-16 NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of360,000). PVP K-15 is also available from ISP Corporation. Other suitable 5 polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.
d) Polyvinyloxazolidone 10 The detergent compositions herein may also utilize polyvinyloxazolidones as polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have an average molecular weight of from 2,500 to 400,000.
e) Polyvinylimidazole The detergent compositions herein may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent. Said polyvinylimidazoles preferably have an average molecular weight of from 2,500 to 400,000.
20 Optical bri~htener The detergent compositions herein also optionally contain from about 0.005% to 5%
by weight of certain types of hydrophilic optical brighteners.
25 Hydrophilic optical brighteners useful herein include those having the structural formula:
N~ ~C=C~N~
R2 SO3M SO3M Rl 30 wherein Rl is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl, R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, CA 0223220~ 1998-03-16 morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.
When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is a 5 cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2-methylaminoand M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt. This particular brightener species is commercially marketed under the 15 tr~den~me Tinopal 5BM-GX by Ciba-Geigy Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener species is 20 commercially marketed under the tr~den~me Tinopal AMS-GX by Ciba Geigy Corporation.
Cationic fabric softening agents 25 Cationic fabric softening agents can also be incorporated into the particle and/or the compositions. Suitable cationic fabric softening agents include the water insoluble tertiary amines or dilong chain amide materials as disclosed in GB-A-I 514 276 and EP-B-0 011 340.
30 Cationic fabric softening agents are typically incorporated at total levels of from 0.5% to 15% by weight, normally from 1% to 5% by weight.
Other optional ingredients CA 0223220~ 1998-03-16 Other optional ingredients suitable for inclusion in the particle and the detergent compositions include perfumes, colours and filler salts, with sodium sulfate being a preferred filler salt.
CA 0223220~ 1998-03-16 pH of the compositions The final detergent compositions preferably have a pH measured as a 1% solution in distilled water of at least 10.0, preferably from 10.0 to 12.5, most preferably from 5 10.5 to 12Ø
Form of the a~glomerated or extruded particle and deter~ent compositions thereof Surfactant a~lomerate particles The particles may take the form of flakes, prills, marumes, noodles, ribbons, but preferably take the form of granules. The most ~l~r~ d way to process the particles, as described above, is by agglomerating or mixing and extruding powders (e.g.
aluminosilicate, optionally carbonate) with high active surfactant pastes and to15 control the particle size of the resultant particles within specified limits.
Form of the compositions The compositions, comprising the particle, can take a variety of physical forms 20 including granular, tablet and bar. The compositions can be of the form of the so-called concentrated granular detergent compositions adapted to be added to a washing m~ ine by means of a dispensing device placed in the machine drum with the soiled fabric load.
25 The mean particle size of the base composition of granular compositions in accordance with the invention can be from 0.1 mm to 5.0 mm, but it should preferably be such that no more that 5% of particles are greater than 1 .7mm in diameter and not more than 5% of particles are less than 0.1 Smm in diameter.
30 The term mean particle size as defined herein is calculated by sieving a sample of the composition into a number of fractions (typically 5 fractions) on a series of Tyler sieves. The weight fractions thereby obtained are plotted against the aperture size of the sieves. The mean particle size is taken to be the aperture size through which 50%
by weight of the sample would pass.
CA 0223220~ 1998-03-16 The bulk density of granular detergent compositions is typically of at least 500g/litre, more preferably from 650 g/litre to 1200 g/litre. Bulk density is measured by means of a simple funnel and cup device consisting of a conical funnel moulded rigidly on a base and provided with a flap valve at its lower extremity to allow the contents of the funnel to be emptied into an axially aligned cylindrical cup disposed below the funnel. The funnel is 130 mm high and has internal diameters of 130 mmand 40 mm at its respective upper and lower extremities. It is mounted so that the lower extremity is 140 mm above the upper surface of the base. The cup has an overall height of 90 mm, an internal height of 87 mm and an internal diameter of 84 10 mm. Its nominal volume is 500 ml.
To carry out a measurement, the funnel is filled with powder by hand pouring, the flap valve is opened and powder allowed to overfill the cup. The filled cup is removed from the frame and excess powder removed from the cup by passing a 15 straight edged implement eg; a knife, across its upper edge. The filled cup is then weighed and the value obtained for the weight of powder doubled to provide a bulk density in g/litre. Replicate measurements are made as required.
Laundry washin~ method Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed thereinan effective amount of a m~rhine laundry detergent composition in accord with the invention. By an effective amount of the detergent composition it is meant from 40g 25 to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional m~rhine laundry methods.
In a plefell~d use aspect a dispensing device is employed in the washing method.30 The dispensing device is charged with the detergent product, and is used to introduce the product directly into the drum of the washing machine before the commencement of the wash cycle. Its volume capacity should be such as to be able to contain sufficient detergent product as would normally be used in the washing method.
35 Once the washing machine has been loaded with laundry the dispensing device containing the detergent product is placed inside the drum. At the commencement of CA 0223220~ 1998-03-16 the wash cycle of the washing machine water is introduced into the drum and the drum periodically rotates. The design of the dispensing device should be such that it permits containment of the dry detergent product but then allows release of thisproduct during the wash cycle in response to its agitation as the drum rotates and also as a result of its contact with the wash water.
To allow for release of the detergent product during the wash the device may possess a number of openings through which the product may pass. Alternatively, the device may be made of a material which is permeable to liquid but impermeable to the solid 10 product, which will allow release of dissolved product. Preferably, the detergent product will be rapidly released at the start of the wash cycle thereby providing transient localised high concentrations of product in the drum of the washing machine at this stage of the wash cycle.
15 Preferred dispensing devices are reusable and are designed in such a way thatcontainer integrity is m~int~ined in both the dry state and during the wash cycle.
Especially preferred dispensing devices for use with the composition of the invention have been described in the following patents; GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-0201376, EP-A-0288345 and EP-A-0288346. An article by J.Bland published 20 in Manufacturing Chemist, November 1989, pages 41-46 also describes especially plcfel~cd dispensing devices for use with granular laundry products which are of a type commonly know as the "granulette". Another plcrellcd dispensing device for use with the compositions of this invention is disclosed in PCT Patent Application No. WO94/11562.
Especially ~;,lefellcid dispensing devices are disclosed in European Patent Application Publication Nos. 0343069 & 0343070. The latter Application discloses a device comprising a flexible sheath in the form of a bag extending from a support ring defining an orifice, the orifice being adapted to admit to the bag sufficient product for 30 one washing cycle in a washing process. A portion of the washing medium flowsthrough the orifice into the bag, dissolves the product, and the solution then passes outwardly through the orifice into the washing medium. The support ring is provided with a m~king arrangement to prevent egress of wetted, undissolved, product, this arrangement typically comprising radially e~t~n~ling walls extending from a central 35 boss in a spoked wheel configuration, or a similar structure in which the walls have a helical form.
CA 0223220~ 1998-03-16 .
Alternatively, the dispensing device may be a flexible container, such as a bag or pouch. The bag may be of fibrous construction coated with a water impermeable protective material so as to retain the contents, such as is disclosed in European published Patent Application No. 0018678. Alternatively it may be formed of a water-insoluble synthetic polymeric material provided with an edge seal or closure designed to rupture in aqueous media as disclosed in European published Patent Application Nos. 0011500, 0011501, 0011502, and 0011968. A convenient form of water frangible closure comprises a water soluble adhesive disposed along and sealing one edge of a pouch formed of a water impermeable polymeric film such aspolyethylene or polypropylene.
Packaging for the compositions Commercially marketed executions of the bleaching compositions can be packaged in any suitable container including those constructed from paper, cardboard, plastic materials and any suitable l~min~tPs A preferred pack~gin~ execution is described in European Application No. 94921505.7.
Abbreviations used in following Examples In the detergent compositions, the abbreviated component identifications have the following m~ninp~
LAS : Sodium linear C12 alkyl benzene sulfonate TAS : Sodium tallow alkyl sulfate C45AS : Sodium C 14-C 15 linear alkyl sulfate CxyEzS : Sodium Clx-Cly branched alkyl sulfate condensed with z moles of ethylene oxide C45E7 : A C14 15 predomin~ntly linear primary alcohol condensed with an average of 7 moles of ethylene oxide C25E3 : A C12 15 branched primary alcohol condensed with an average of 3 moles of ethylene oxide C25E5 : A C12 15 branched primary alcohol condensed with an average of 5 moles of ethylene oxide CA 0223220~ 1998-03-16 CEQ : RlCOOCH2CH2.N+(CH3)3 with Rl = C11-C13 QAS : R2.N+(CH3)2(c2H4OH) with R2 = C12 ~ C14 Soap : Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut oils.
TFAA : C 16-c 18 alkyl N-methyl glucamide TPKFA : C12-C14 topped whole cut fatty acids STPP : Anhydrous sodium tripolyphosphate Zeolite A : Hydrated Sodium Aluminosilicate of formula Nal2(A102SiO2)12. 27H20 having a primary particle size in the range from 0.1 to 10 micrometers NaSKS-6 : Crystalline layered silicate of formula o -Na2Si205 Citric acid : Anhydrous citric acid Carbonate : Anhydrous sodium carbonate with a particle size between 200 ~lm and 900~1m Bicarbonate : Anhydrous sodium bicarbonate with a particle size distribution between 40011m and 1200~1m Silicate : Amorphous Sodium Silicate (SiO2:Na2O; 2.0 ratio) Sodium sulfate : Anhydrous sodium sulfate Citrate : Tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution between 425~1m and 850~m MA/AA : Copolymer of 1 :4 maleic/acrylic acid, average molecular weight about 70,000.
CMC : Sodium carboxymethyl cellulose Protease : Proteolytic enzyme of activity 4KNPU/g sold by NOVO Industries A/S under the tradename Savinase Alcalase : Proteolytic enzyme of activity 3AU/g sold by NOVO Industries A/S
Cellulase : Cellulytic enzyme of activity 1000 CEVU/g sold by NOVO Industries A/S under the tr~dçn~me Carezyme Amylase : Amylolytic enzyme of activity 60KNU/g sold by NOVO Industries A/S under the tradename Termamyl 60T
CA 0223220~ 1998-03-16 Lipase : Lipolytic enzyme of activity 1 00kLU/g sold by NOVO Industries A/S under the tradename Lipolase Endolase : Endoglunase enzyme of activity 3000 CEVU/g sold by NOVO Industries A/S
PB4 : Sodium perborate tetrahydrate of nominal formula NaB02.3H20-H202 PB 1 : Anhydrous sodium perborate monohydrate bleach of nominal formula NaBo2.H2o2 Percarbonate : Sodium Percarbonate of nominal formula 2Na2C03 3H202 NOBS : Nonanoyloxybenzene sulfonate in the forrn of the sodium salt.
TAED : Tetraacetylethylene~ mine DTPMP: Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Trade name Dequest 2060 Photoactivated : Sulfonated Zinc Phthlocyanine encapsulated in bleach dextrin soluble polymer Brightener l : Disodium4,4'-bis(2-sulphostyryl)biphenyl Brightener 2 : Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2-yl)amino) stilbene-2:2'-disulfonate.
HEDP : 1,1-hydroxyethane diphosphonic acid PVNO : Polyvinylpyridine N-oxide PVPVI : Copolymer of polyvinylpyrolidone and vinylimidazole SRP 1 : Sulfobenzoyl end capped esters with oxyethylene oxy and terephtaloyl backbone SRP 2 : Diethoxylated poly (1, 2 propylene terephtalate) short block polymer Silicone antifoam: Polydimethylsiloxane foam controller with siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1.
Alkalinity : % weight equivalent of NaOH, as obtained using the alkalinity release test method described herein.
CA 0223220~ 1998-03-16 In the following Examples all levels are quoted as % by weight of the composition:
Example 1 The following detergent formulations according to the present invention were prepared:
A B
Blown Powder Zeolite A 15.0 Sodium sulfate - -LAS 3.0 CEQ 2.0 1.3 DTPMP 0.4 CMC 0.4 MA/AA 4.0 Agglomerates PB1 15.0 10.0 C45AS - 11.0 LAS 6.0 TAS 3.0 Silicate 4.0 Zeolite A 10.0 13.0 MA/AA - 2.0 Citric Acid 4.0 3.0 Spray On Perfume 0.3 0.5 C 45 E 7 4.0 4.0 C 25 E3 2.0 2.0 Dry additives T A E D 4.0 2.0 MA/AA - 3.0 NaSKS-6 - 12.0 Bicarbonate 7.0 5.0 Carbonate 17.0 14.0 PVPVI/PVNO 0.5 0.5 Alcalase 0.5 0.9 Lipase 0.4 0.4 Amylase 0.6 0.6 Cellulase 0.6 0.6 Silicone antifoam 5.0 5.0 Dry additives Sodiurn sulfate 0.0 2.0 Balance (Moisture and Miscellaneous) 100.0 100.0 Density (g/litre) 700 700 CA 0223220~ 1998-03-16 Example 2 The following high density and bleach-cont~ining detergent formulations, according to the present invention were prepared:
C D
Blown Powder Zeolite A 15.0 15.0 Sodium sulfate 0.0 0.0 LAS 3.0 3.0 QAS - 1.5 CEQ 2.0 2.0 DTPMP 0.4 0.4 CMC 0.4 0.4 MA/AA 4.0 2.0 Agglomerates PB1 15.0 15.0 LAS 4.0 4.0 TAS 2.0 1.0 C24E5 2.0 2.0 Silicate 3.0 4.0 Citric Acid 2.0 3.0 Zeolite A 8.0 8.0 Carbonate - 6.0 Magnesium sulphate 0.3 0.4 Spray on Perfume 0.3 0.3 C45E7 2.0 2.0 Dry additives Citrate 5.0 2.0 Bicarbonate Carbonate 16.0 10.0 TAED 6.0 5.0 Polyethylene oxide of MW 5,000,000 - 0.2 Bentonite clay - 10.0 Protease 1.0 1.0 Lipase 0.4 0.4 Amylase 0.6 0.6 Cellulase 0.6 0.6 Silicone antifoam 5.0 5.0 Dry additives Sodium sulfate 0.0 0.0 Balance (Moisture and 100.0 100.0 Miscellaneous) Density (g/litre) 850 850 CA 0223220~ 1998-03-16 Example 3 The following high density detergent formulations, according to the present invention were prepared:
E F
Agglomerate LAS 7.5 PB1 12.0 PB4 - 15.0 C45AS - 14.0 CEQ - 3.5 Zeolite A 15.0 citric acid 1.5 2.0 Carbonate 4.0 MA/AA 4.0 2.0 CMC 0.5 0.5 DTPMP 0.4 0.4 C24E5 5.0 5.0 Spray On Perfume 0.5 0.5 Dry Additives Zeolite - 6.0 HEDP 0.5 0.3 SKS 6 13.0 10.0 Citrate 3.0 1.0 TAED 5.0 7.0 Percarbonate 20.0 20.0 SRP 1 0.3 0.3 Protease 1.4 1.4 Lipase 0.4 0.4 Cellulase 0.6 0.6 Arnylase 0.6 0.6 Silicone antifoarn 5.0 5.0 Brightener 1 0.2 0.2 Brightener 2 0.2 Balance (Moisture and 100 100 Miscellaneous) Density (g/litre) 850 850
Claims (21)
1. An agglomerate or extruded detergent particle comprising one or more surfactants, an acid source and a perborate component.
2. A detergent particle according to claim 1 wherein said acid source is present at a level of from 3% to 30% by weight of the particle.
3. A detergent particle according to claim 1 wherein said acid source is present at a level of from 7% to 15% by weight of the particle.
4. A detergent particle according to claim 1 wherein said surfactant is present at a level of from 25% to 60% by weight of the particle.
5. A detergent particle according to claim 1 wherein said perborate bleach is present at a level of from 15% to 50% by weight of the particle.
6. A detergent particle according to claim 1 wherein said perborate bleach is in the form of a monohydrate.
7. A detergent particle according to claim 1 wherein said perborate bleach is in the form of a tetrahydrate.
8. A detergent particle according to claim 1 wherein the surfactant comprises one or more anionic and nonionic surfactants
9. A detergent particle according to claim 1 wherein said acid source comprises an organic acid.
10. A detergent particle according to claim 1 wherein the acid source is citric acid.
11. A detergent particle according to claim 1 which is substantially free from bleach activator and which contains alkaline crystalline layered silicate.
12. A detergent particle according to claim 1 wherein magnesium sulphate is present at a level of from 0.3% to 3% by weight of the particle.
13. A detergent composition comprising the detergent particle according to claim 1 and an alkali source.
14. A detergent composition according to claim 13 wherein said alkali source comprises an alkaline salt selected from an alkali metal or alkaline earth metalcarbonate, bicarbonate or sesqui-carbonate.
15. A detergent composition according to claim 13 wherein the alkali source is present in an amount of from about 2 % to about 75 % by weight of the composition.
16. A detergent composition according to claim 13 wherein the alkali source is present in an amount of from about 10% to about 30% by weight of the composition.
17. A process for making an agglomerated detergent particle according to claim 1 comprising the steps of:
i) admixing one or more detergent surfactants, the perborate bleach and an acid source to form a mixture; and ii) agglomerating the mixture to form agglomerated particles.
i) admixing one or more detergent surfactants, the perborate bleach and an acid source to form a mixture; and ii) agglomerating the mixture to form agglomerated particles.
18. A process according to Claim 17 for making an agglomerated detergent particle according to any of claims 1 to 10, wherein in step i) the acid source and one or more surfactants are mixed prior to addition of the perborate bleach.
19. A process for making the extruded detergent particle according to claim 1 by extrusion, the process comprising forcing a paste, comprising the acid source, surfactant and perborate component under pressure through holes of an extruder, whereafter the extruded paste is cut into particles.
20. A process according to claim 19 whereby said paste comprises at least two pre-mixed pastes, comprising a first pre-mixed paste which comprises the acid source and a second pre-mixed paste whicho comprises the perborate component.
21. A method of washing laundry in a domestic washing machine comprising, introducing into a dispensing device which is placed in the drum of the washing machine, or introducing into the dispensing drawer of a washing machine, an effective amount of a detergent composition of claim 13.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP9705840.8 | 1997-03-20 | ||
GB9705840A GB2323384A (en) | 1997-03-20 | 1997-03-20 | A detergent composition |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2232205A1 true CA2232205A1 (en) | 1998-09-20 |
Family
ID=10809612
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA 2232205 Abandoned CA2232205A1 (en) | 1997-03-20 | 1998-03-16 | Detergent particle |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0866118A3 (en) |
CA (1) | CA2232205A1 (en) |
GB (1) | GB2323384A (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU1449100A (en) * | 1998-10-26 | 2000-05-15 | Procter & Gamble Company, The | Detergent particles and processes for making them |
DE19854083A1 (en) * | 1998-11-24 | 2000-05-25 | Henkel Kgaa | Detergent containing citric acid |
EP1048715A1 (en) * | 1999-04-30 | 2000-11-02 | The Procter & Gamble Company | Method of dispensing a detergent composition |
EP1048712A1 (en) * | 1999-04-30 | 2000-11-02 | The Procter & Gamble Company | A process of treating fabrics with a laundry detergent additive tablet |
EP1048714A1 (en) * | 1999-04-30 | 2000-11-02 | The Procter & Gamble Company | Method of dispensing a detergent composition |
US6491947B2 (en) | 2000-11-03 | 2002-12-10 | Chemlink Laboratories, Llc | Expanded perborate salt, use, and method of production |
US6541439B1 (en) * | 2001-11-16 | 2003-04-01 | Colgate-Palmolive Company | Cleaning system including a powdered cleaning composition disposed in a water soluble container |
EP1633847A4 (en) * | 2003-05-30 | 2007-04-11 | Church & Dwight Co Inc | Detergent formulations containing alkaline peroxide salts and organic acids |
DE102007008655A1 (en) † | 2007-02-20 | 2008-08-21 | Henkel Ag & Co. Kgaa | Siderophore-metal complexes as bleach catalysts |
GB0805908D0 (en) * | 2008-04-01 | 2008-05-07 | Reckitt Benckiser Inc | Laundry treatment compositions |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4252664A (en) * | 1978-10-30 | 1981-02-24 | Colgate-Palmolive Company | Effervescent granules |
US4540504A (en) * | 1983-04-22 | 1985-09-10 | Warner-Lambert Company | Denture cleaner having improved dissolution time and clarity and method of preparation |
JPS63199796A (en) * | 1987-02-16 | 1988-08-18 | 花王株式会社 | High density granular detergent composition |
EP0296813A1 (en) * | 1987-06-24 | 1988-12-28 | Imperial Chemical Industries Plc | Powder compositions and detergent compositions |
EP0483413B1 (en) * | 1990-10-30 | 1996-01-31 | The Procter & Gamble Company | Improving the colour of surfactant agglomerates by admixing a solid bleaching agent |
WO1992018596A1 (en) * | 1991-04-19 | 1992-10-29 | The Procter & Gamble Company | Granular laundry detergent compositions having improved solubility |
GB9120657D0 (en) * | 1991-09-27 | 1991-11-06 | Unilever Plc | Detergent powders and process for preparing them |
CA2141587A1 (en) * | 1992-08-01 | 1994-02-17 | Anthony Dovey | Low gelling detergent compositions and a process for making such compositions |
EP0754218B1 (en) * | 1994-04-07 | 1998-09-02 | The Procter & Gamble Company | Bleach compositions comprising metal-containing bleach catalysts and antioxidants |
DE19509752A1 (en) * | 1995-03-17 | 1996-09-19 | Henkel Kgaa | Compressed washing and cleaning agents with high powder density |
GB2315761A (en) * | 1996-07-31 | 1998-02-11 | Procter & Gamble | Detergent composition comprising a particulate acid source and an alkaline source |
WO1998004668A1 (en) * | 1996-07-31 | 1998-02-05 | The Procter & Gamble Company | A detergent composition |
-
1997
- 1997-03-20 GB GB9705840A patent/GB2323384A/en not_active Withdrawn
-
1998
- 1998-03-09 EP EP98200736A patent/EP0866118A3/en not_active Withdrawn
- 1998-03-16 CA CA 2232205 patent/CA2232205A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
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GB2323384A (en) | 1998-09-23 |
GB9705840D0 (en) | 1997-05-07 |
EP0866118A3 (en) | 1998-12-16 |
EP0866118A2 (en) | 1998-09-23 |
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